Alkylation of aromatic compounds using a sol-gel derived porous microcomposite of perfluorinated ion-exchange polymer and metal oxide

ABSTRACT

Porous microcomposites have been prepared from perfluorinated ion-exchange polymer and metal oxides such as silica using the sol-gel process. Such microcomposites possess high surface area and exhibit extremely high catalytic activity. The microcomposites catalyze, among others, the reaction between organic aromatic compounds and olefins.

This is a division of application Ser. No. 09/121,106, filed Jul. 23,1998 U.S. Pat. No. 5,948,946 which is a division of application Ser. No.08/574,751, filed Dec. 19, 1995 now U.S. Pat. No. 5,824,622, which is acontinuation-in-part of application Ser. No. 08/362,063, filed Dec. 22,1994, abandoned, which is a continuation-in-part of application Ser. No.08/180,250, filed Jan. 12, 1994, now abandoned.

FIELD OF THE INVENTION

This invention relates to porous microcomposites comprisingperfluorinated ion-exchange polymers (PFIEP) containing pendant sulfonicacid groups and/or pendant carboxylic acid groups entrapped within andhighly dispersed throughout a metal oxide network, prepared using asol-gel process. Due to their high surface area and acid functionalitythese microcomposites possess wide utility as improved solid acidcatalysts.

TECHNICAL BACKGROUND

U.S. Pat. No. 5,252,654 discloses polymeric composites comprising aninterpenetrating network of an organic polymer and an inorganic glassypolymer and a process for making such composites. The disclosed materialis nonporous, and the use of perfluorinated ion-exchange polymers(PFIEP) containing pendant sulfonic acid groups or pendant carboxylicacid groups is not disclosed.

K. A. Mauritz et al., Polym. Mater. Sci. Eng. 58, 1079-1082(1988), in anarticle titled "Nafion-based Microcomposites: Silicon Oxide-filledMembranes", discuss the formation of micro composite membranes by thegrowth of silicon oxide microclusters or continuous silicon oxideinterpenetrating networks in pre-swollen "NAFION®" sulfonic acid films."NAFION®" is a registered trademark of E. I. du Pont de Nemours andCompany.

U.S. Pat. No. 5,094,995 discloses catalysts comprising perfluorinatedion-exchange polymers (PFIEP) containing pendant sulfonic acid groupssupported on an inert carrier having a hydrophobic surface comprisingcalcined shot coke.

U.S. Pat. No. 4,038,213 discloses the preparation of catalystscomprising perfluorinated ion-exchange polymers (PFIEP) containingpendant sulfonic acid groups on a variety of supports.

The catalytic utility of perfluorinated ion-exchange polymers (PFIEP)containing pendant sulfonic acid groups, supported and unsupported hasbeen broadly reviewed: G. A. Olah et al., Synthesis, 513-531(1986) andF. J. Waller, Catal. Rev.-Sci. Eng., 1-12(1986).

SUMMARY OF THE INVENTION

This invention provides a porous microcomposite comprisingperfluorinated ion-exchange polymer containing pendant sulfonic and/orcarboxylic acid groups entrapped within and highly dispersed throughouta network of metal oxide, wherein the weight percentage ofperfluorinated ion-exchange polymer in the microcomposite is from about0.1 to 90 percent, preferably from about 5 to about 80 percent, andwherein the size of the pores in the microcomposite is about 0.5 nm toabout 75 nm.

In a separate embodiment, the microcomposite can simultaneously containlarger pores ranging from about 75 nm to about 1000 nm, wherein theselarger pores are formed by introducing acid-extractable filler particlesduring the formation process.

This invention further provides the process of preparation of a porousmicrocomposite which comprises perfluorinated ion-exchange polymercontaining pendant sulfonic and/or carboxylic acid groups entrappedwithin and highly dispersed throughout a network of metal oxide, whereinthe weight percentage of perfluorinated ion-exchange polymer in themicrocomposite is from about 0.1 to 90 percent, and wherein the size ofthe pores in the microcomposite is about 0.5 nm to about 75 nm;

said process comprising the steps of:

a. mixing the perfluorinated ion-exchange polymer with one or more metaloxide precursors in a common solvent;

b. initiating gelation;

c. allowing sufficient time for gelation and aging of the mixture; and

d. removing the solvent.

In a further preferred embodiment the process further comprises at step(a), adding to the mixture an amount from about 1 to 80 weight percentof an acid extractable filler particle, after d;

e. acidifying the product of step d by the addition of acid; and

f. removing the excess acid from the microcomposite;

to yield a microcomposite further containing pores in the range of about75 nm to about 1000 nm.

The present invention also provides an improved process for thenitration of an aromatic compound wherein the improvement comprisescontacting said aromatic compound with a catalytic microcomposite of thepresent invention, described above.

The present invention further provides an improved process for theesterification of a carboxylic acid with an olefin wherein theimprovement comprises contacting said carboxylic acid with a catalyticmicrocomposite of the present invention, described above.

The present invention also provides an improved process for thepolymerization of tetrahydrofuran wherein the improvement comprisescontacting said tetrahydrofuran with a catalytic microcomposite of thepresent invention, described above.

The present invention further provides an improved process for thealkylation of an aromatic compound with an olefin wherein theimprovement comprises contacting said aromatic compound with a catalyticmicrocomposite of the present invention, described above.

The present invention provides an improved process for the acylation ofan aromatic compound with an acyl halide wherein the improvementcomprises contacting said aromatic compound with a catalyticmicrocomposite of the present invention, described above.

The present invention further provides an improved process for thedimerization of an alpha substituted styrene, wherein the improvementcomprises contacting said alpha substituted styrene with a catalyticmicrocomposite of the present invention, described above.

The present invention further provides a process for regenerating acatalyst comprising a microcomposite of the present invention, asdescribed above, comprising the steps of: mixing the microcomposite withan acid, and removing the excess acid.

The present invention also provides a process for the isomerization ofan olefin comprising contacting said olefin at isomerization conditionswith a catalytic amount of a porous microcomposite, said microcompositecomprising perfluorinated ion-exchange polymer containing pendantsulfonic and/or carboxylic acid groups entrapped within and highlydispersed throughout a network of metal oxide, wherein the weightpercentage of perfluorinated ion-exchange polymer in the microcompositeis from about 0.1 to 90 percent, preferably from about 5 to about 80percent, most preferably from about 5 to about 20 percent and whereinthe size of the pores in the microcomposite is about 0.5 nm to about 75nm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing data from Example 58 and Table 4b which showsthe effect of contact time at 50° C. and He/1-butene=1.2/1.0 on 1-buteneisomerization over a 13 wt % "NAFION®" PFIEP/silica microcompositeprepared as in Example 16.

DETAILED DESCRIPTION OF THE INVENTION

The organic-inorganic polymer microcomposites of the present inventionare high surface area, porous microcompositions which exhibit excellentcatalytic activity. Whereas the surface area of "NAFION®" NR 50 PFIEP, acommercial product, is approximately 0.02 m² per gram, a preferredembodiment of the present invention comprises microcomposites of PFIEPand silica having a surface area typically of 5 to 500 m² per gram. Thecomposition of the present invention exists as a particulate solid whichis porous and glass-like in nature, typically 0.1-4 mm in size andstructurally hard, similar to dried silica gels. The perfluorinated ionexchange polymer (PFIEP) is highly dispersed within and throughout thesilica network of the microcomposite of the present invention, and themicrostructure is very porous. The porous nature of this material isevident from the high surface areas measured for these glass-likepieces, having typical pore diameters in the range of 1-25 nm. Anotherpreferred embodiment is the use of the present invention in pulverizedform.

In another preferred embodiment, macroporosity (pore sizes about 75 toabout 1000 nm) is also introduced into the microcomposite, resulting ina microcomposite having both increased surface area from the microporesand mesopores (0.5-75 nm) and enhanced accessibility resulting from themacropores (75-1000 nm).

Perfluorinated ion-exchange polymers (PFIEP) containing pendant sulfonicacid, carboxylic acid, or sulfonic acid and carboxylic acid groups usedin the present invention are well known compounds. See, for example,Waller et al., Chemtech, July, 1987, pp. 438-441, and referencestherein, and U.S. Pat. No. 5,094,995, incorporated herein by reference.Perfluorinated ion-exchange polymers (PFIEP) containing pendantcarboxylic acid groups have been described in U.S. Pat. No. 3,506,635,which is also incorporated by reference herein. Polymers discussed by J.D. Weaver et al., in Catalysis Today, 14 (1992) 195-210, are also usefulin the present invention. Polymers that are suitable for use in thepresent invention have structures that include a substantiallyfluorinated carbon chain that may have attached to it side chains thatare substantially fluorinated. In addition, these polymers containsulfonic acid groups or derivatives of sulfonic acid groups, carboxylicacid groups or derivatives of carboxylic acid groups and/or mixtures ofthese groups. For example, copolymers of a first fluorinated vinylmonomer and a second fluorinated vinyl monomer having a pendant cationexchange group or a pendant cation exchange group precursor can be used,e.g., sulfonyl fluoride groups (SO₂ F) which can be subsequentlyhydrolyzed to sulfonic acid groups. Possible first monomers includetetrafluoroethylene (TFE), hexafluoropropylene, vinyl fluoride,vinylidine fluoride, trifluoroethylene, chlorotrifluoroethylene,perfluoro (alkyl vinyl ether), and mixtures thereof. Possible secondmonomers include a variety of fluorinated vinyl ethers with pendantcation exchange groups or precursor groups. Preferably, the polymercontains a sufficient number of acid groups to give an equivalent weightof from about 500 to 20,000, and most preferably from 800 to 2000.Representative of the perfluorinated polymers for use in the presentinvention are "NAFION®" PFIEP (a family of polymers for use in themanufacture of industrial chemicals, commercially available from E. I.du Pont de Nemours and Company), and polymers, or derivatives ofpolymers, disclosed in U.S. Pat. Nos. 3,282,875; 4,329,435; 4,330,654;4,358,545; 4,417,969; 4,610,762; 4,433,082; and 5,094,995. Morepreferably the polymer comprises a perfluorocarbon backbone and apendant group represented by the formula --OCF₂ CF(CF₃)OCF₂ CF₂ SO₃ X,wherein X is H, an alkali metal or NH₄. Polymers of this type aredisclosed in U.S. Pat. No. 3,282,875.

Typically, suitable perfluorinated polymers are derived from sulfonylgroup-containing polymers having a fluorinated hydrocarbon backbonechain to which are attached the functional groups or pendant side chainswhich in turn carry the functional groups. Fluorocarbosulfonic acidcatalysts polymers useful in preparing the microcomposites of thepresent invention have been made by Dow Chemical and are described inCatalyis Today, 14 (1992) 195-210. Other perfluorinated polymer sulfonicacid catalysts are described in Synthesis, G. I. Olah, P. S. Iyer, G. K.Surya Prakash, 513-531 (1986).

There are also several additional classes of polymer catalystsassociated with metal cation ion-exchange polymers and useful inpreparing the microcomposite of the present invention. These comprise 1)a partially cation-exchanged polymer, 2) a completely cation-exchangedpolymer, and 3) a cation-exchanged polymer where the metal cation iscoordinated to another ligand (see U.S. Pat. No. 4,414,409, and Waller,F. J. In Polymeric Reagents and Catalysts; Ford, W. T., Ed.,; ACSSymposium Series 308; American Chemical Society; Washington, DC, 1986,Chapter 3).

Preferred PFIEP suitable for use in the present invention comprise thosecontaining sulfonic acid groups. Most preferred is a sulfonated"NAFION®" PFIEP.

Perfluorinated ion-exchange polymers are used within the context of theinvention in solution form. It is possible to dissolve the polymer byheating it with an aqueous alcohol to about 240° C. or higher forseveral hours in a high pressure autoclave (see U.S. Pat. No. 4,433,082or Martin et al., Anal. Chem., Vol. 54, pp 1639-1641 (1982). Othersolvents and mixtures may also be effective in dissolving the polymer.

Ordinarily, for each part by weight of polymer employed to be dissolved,from as little as about 4 or 5 parts by weight up to about 100 parts byweight, preferably 20-50 parts by weight, of the solvent mixture areemployed. In the preparation of the dissolved polymer, there is aninteraction between the equivalent weight of the polymer employed, thetemperature of the process, and the amount and nature of the solventmixture employed. For higher equivalent weight polymers, the temperatureemployed is ordinarily higher and the amount of liquid mixture employedis usually greater.

The resulting mixture can be used directly and may be filtered throughfine filters (e.g., 4-5.5 micrometers) to obtain clear, though perhapsslightly colored, solutions. The mixtures obtained by this process canbe further modified by removing a portion of the water, alcohols andvolatile organic by-products by distillation.

Commercially available solutions of perfluorinated ion-exchange polymerscan also be used in the preparation of the microcomposite of the presentinvention (e.g., at 5 wt % solution of a perfluorinated ion-exchangepowder in a mixture of lower aliphatic alcohols and water, Cat. No.27,470-4, Aldrich Chemical Company, Inc., 940 West Saint Paul Avenue,Milwaukee, Wis. 53233).

"Metal oxide" signifies metallic or semimetallic oxide compounds,including, for example, alumina, silica, titania, germania, zirconia,alumino-silicates, zirconyl-silicates, chromic oxides, germanium oxides,copper oxides, molybdenum oxides, tantalum oxides, zinc oxides, yttriumoxides, vanadium oxides, and iron oxides. Silica is most preferred. Theterm "metal oxide precursor" refers to the form of the metal oxide whichis originally added in the sol-gel process to finally yield a metaloxide in the final microcomposite. In the case of silica, for example,it is well known that a range of silicon alkoxides can be hydrolyzed andcondensed to form a silica network. Such precursors astetramethoxysilane (tetramethyl orthosilicate), tetraethoxysilane(tetraethyl orthosilicate), tetrapropoxysilane, tetrabutoxysilane, andany compounds under the class of metal alkoxides which in the case ofsilicon is represented by Si(OR)₄, where R includes methyl, ethyl,n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or whereR is a range of organic groups, such as alkyl. Also included as aprecursor form is silicon tetrachloride. Further precursor formscomprise organically modified silica, for example, CH₃ Si(OCH₃)₃,PhSi(OCH₃)₃, and (CH₃)₂ Si(OCH₃)₂. Other network formers include metalsilicates, for example, potassium silicate, sodium silicate, lithiumsilicate. K, Na or Li ions can be removed using a DOWEX® cation exchangeresin (sold by Dow Chemical, Midland, Mich., which generates polysilicicacid which gels at slightly acid to basic pH. The use of "LUDOX®"colloidal silica (E. I. du Pont de Nemours and Company, Wilmington,Del.) and fumed silica ("CAB-O-SIL®" sold by Cabot Corporation ofBoston, Mass.) which can be gelled by altering pH and adjusting theconcentration in solution will also yield a metal oxide network in themicrocomposite of the invention. For example, typical precursor forms ofsilica are Si(OCH₃)₄, Si(OC₂ H₅)₄ and Na₂ SiO₃ ; and a typical precursorform of alumina is aluminum tri-secbutoxide Al(OC₄ H₉)₃.

"Acid extractable filler particles" which are used in the process of theinvention to introduce macropores of about 75 to about 1000 nm into themicrocomposite include particles which are insoluble in the preparativegel-forming solvent, but are acid soluble and extractable from theformed microcomposite. Such filler particles include, for example,alkali metal carbonates or alkaline earth carbonates, such as calciumcarbonate, sodium carbonate and potassium carbonate.

The first stage of the process for the preparation of the microcompositeof the present invention involves preparing a gel solution that containsboth the perfluorinated ion-exchange polymer (PFIEP) containing pendantsulfonic acid groups and/or pendant carboxylic acid groups and one ormore metal oxide precursors in a common solvent.

This solvent normally comprises water and various lower aliphaticalcohols such as methanol, 1-propanol, 2-propanol, mixed ethers andn-butanol. Thus, in some cases the water necessary for gel formation canbe supplied by the water in the reaction solvent. Other polar solventswhich may be suitable for the particular metal oxide precursor/polymerselected include acetonitrile, dimethyl formamide, dimethylsulfoxide,nitromethane, tetrahydrofuran and acetone. Toluene, alkanes andfluorocarbon-containing solvents can also be useful in some instances tosolubilize the polymer.

Gelation may in some instances self-initiate, for example, when water ispresent in the common solvent, or via rapid drying, such as spraydrying. In other instances, gelation must be initiated, which can beachieved in a number of ways depending on the initial mixture ofpolymer, metal oxide precursor and solvent selected. Gelation isdependent on a number of factors such as the amount of water present,because water is required for the hydrolysis and condensation reaction.Other factors include temperature, solvent type, concentrations, pH,pressure and the nature of the acid or base used. The pH can be achievedin a number of ways, for example, by adding base to the PFIEP solutionor by adding the PFIEP solution to the base, or by adding the metaloxide to the solution than adjusting pH with acid or base. Anothervariable in addition to the mode of addition for achievement of pH isthe concentration of base employed. Gels can also be formed by acidcatalyzed gellation. See Sol-Gel Science, Brinker, C. J. and Scherer, G.W., Academic Press, 1990. Non-gelled PFIEP/metal oxide solution may bespray dried to yield dried PFIEP/metal oxide composites.

Time required for the gel forming reaction can vary widely depending onfactors such as acidity, temperature, and concentration. It can varyfrom practically instantaneous to several days.

The gel forming reaction can be carried out at virtually any temperatureat which the solvent is in liquid form. The reaction is typicallycarried out at room temperature.

Pressure over the gel forming reaction is not critical and may varywidely. Typically the reaction is carried out at atmospheric pressure.The gel forming reaction can be carried out over a wide range of acidityand basicity depending upon the amount of base added to the gelprecursor.

After formation, but before isolation, the gel, still in the presence ofits reaction solvent, may be allowed to stand for a period of time. Thisis referred to as aging.

The product is dried at room temperature or at elevated temperatures inan oven for a time sufficient to remove solvent. Drying can be doneunder vacuum, or in air or using an inert gas such as nitrogen.Optionally, after aging and/or removal of the solvent, the hardglass-like product can be ground and passed through a screen, preferablya 10-mesh screen. Grinding generates smaller particles (and greatersurface area) which are more readily re-acidified. Grinding isespecially useful for microcomposites having a high weight percent ofPFIEP.

Preferably, following removal of the solvent and optional grinding, thematerial is reacidified, washed and filtered. This may be repeated anumber of times. Reacidification of the material converts, for example,the sodium salt of the perfluorosulfonic acid into the acidic, activeform. Suitable acids comprise HCl, H₂ SO₄ and nitric acid.

A number of reaction variables, for example acidity, basicity,temperature, aging, method of drying and drying time of gels, have beenfound to affect the pore size and pore size distribution. Both higher pHand longer aging of gels (before solvent removal) lead to larger finalpore size in the dried PFIEP/metal oxide gels. Pore size can be variedover a wide range (about 0.5 to about 75 nm) depending on the variablesdescribed above. Aging of the wet gels (in the presence of the solvent)for a few hours at 75° C. also leads to an increase in pore sizealthough over a smaller range. This effect is characteristic of silicatype gels, where the aging effect gives rise to an increasingly crosslinked network which upon drying is more resistant to shrinkage and thusa higher pore size results. See, for example, the text Sol-Gel Science,Brinker, C. J. and Scherer, G. W., Academic Press, 1990, pp. 518-523. Inthe present invention, preferred pore size is about about 0.1 nm toabout 75 nm, more preferred about 0.5 to about 50 nm, most preferred isabout 0.5 to about 30 nm.

Microcomposites comprising macropores (about 75 to about 1000 nm) havealso been developed hereunder which have both high surface area andmicro-, meso- and macroporosity. Such a structure is easily accessiblefor catalytic and ion exchange purposes. This unique microstructure ofthe present invention is prepared by adding sub-micron size particles ofcalcium carbonate to a PFIEP/metal oxide precursor solution prior to thegelation step. Upon acidification of the glass gels, the calciumcarbonate dissolves out leaving large (about 500 nm) pores connectedthroughout the matrix with a sub-structure of about 10 nm micropores.This kind of structure offers a high surface area PFIEP/metal oxidenetwork within the microcomposite which is readily accessiblethroughout. Macroporosity can be achieved by adding approximately 1 to80 wt % (based upon gel weight) of acid-extractable filler particlessuch as calcium carbonate, to the sol-gel process prior to the gelationstep.

It is believed that the highly porous structure of the microcompositesof the present invention consists of a continuous metal oxide phasewhich entraps a highly dispersed PFIEP within and throughout a connectednetwork of porous channels. The porous nature of the material can bereadily demonstrated, for example, by solvent absorption. Themicrocomposite can be observed to emit bubbles which are evolved due tothe displacement of the air from within the porous network.

The distribution of the PFIEP entrapped within and throughout the metaloxide is on a very fine sub-micron scale. The distribution can beinvestigated using electron microscopy, with energy dispersive X-rayanalysis, which provides for the analysis of the elements Si and O (whenusing silica, for example) and C and F from the PFIEP fluoropolymer.Fractured surfaces within a particle and several different particles forcompositions ranging from 10 to 40 wt % "NAFION®" PFIEP were analyzed,and all of the regions investigated showed the presence of both thesilica and PFIEP polymer from the edge to the center of themicrocomposite particles; thus the microcomposite exhibited an intimatemixture of Si and F. No areas enriched in entirely Si or entirely F wereobserved, rather a uniform distribution of Si and F was seen. Thisbicomponent description is believed to be accurate for areas as low 0.1micrometer in size. The morphology of the microcomposites, as preparedby Example 1, is somewhat particulate in nature, again as observed usingscanning electron microscopy. This is typical of silica gel typematerial prepared using this sol-gel procedure. The primary particlesize is on the order of 5-10 nm. This was also confirmed using smallangle x-ray scattering experiments on the material, which revealed adomain size in the range of 5-10 nm. The data is consistent with thePFIEP being entrapped within and highly dispersed throughout the silica.

The microcomposites of the invention are useful as ion exchange resins,and as catalysts, for example, for alkylating aliphatic or aromatichydrocarbons, for decomposing organic hydroperoxides, such as cumenehydroperoxide, for sulfonating or nitrating organic compounds, and foroxyalkylating hydroxylic compounds. A serious drawback to the commercialuse of previous perfluorocarbon sulfonic acid catalysts has been theirhigh cost and relatively low catalytic activity. The present inventionprovides the benefits of reduced costs, higher catalytic activity, andin some cases improved reaction selectivity. Other commerciallyimportant applications for PFIEP/silica catalysts of the presentinvention comprise hydrocarbon isomerizations and polymerizations;carbonylation and carboxylation reactions; hydrolysis and condensationreactions, esterifications and etherification; hydrations andoxidations; aromatic acylation, alkylation and nitration; andisomerization and metathesis reactions.

The present invention provides an improved process for the nitration ofan aromatic compound wherein the improvement comprises contacting thearomatic compound with a microcomposite of the present invention as acatalyst. For example, in the nitration of benzene, a solutioncomprising benzene and optionally, a desiccant such as MgSO₄, is heated,typically to reflux at atmospheric pressure under an inert atmosphere,and a nitrating agent, for example, HNO₃ is added. The process isconducted under normal nitration conditions which conditions, such astemperature, are dependent upon the reactivity of the aromatic used.When a microcomposite of the present invention is used as a catalyst inthe benzene solution, a high rate of conversion and selectivity tonitrobenzene is demonstrated as compared to "NAFION®" PFIEP alone or tothe use of no catalyst (see Table I, Example 42). A preferred catalystfor this process is a microcomposite of the present invention whereinthe perfluorinated ion-exchange polymer contains pendant sulfonic acidgroups and wherein the metal oxide is silica, alumina, titania,germania, zirconia, alumino-silicate, zirconyl-silicate, chromic oxideand/or iron oxide. Most preferred is wherein the perfluorinatedion-exchange polymer is a "NAFION®" PFIEP and the metal oxide is silica,the most preferred "NAFION®" PFIEP having approximately 6.3tetrafluoroethylene (TFE) molecules for every perfluoroperfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule (CF₂═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) and an equivalentweight of approximately 1070.

The present invention further provides an improved process for theesterification of a carboxylic acid by reaction with an olefin whereinthe improvement comprises contacting said carboxylic acid with a porousmicrocomposite of the present invention as a catalyst. For example, theesterification of acetic acid with cyclohexene to yieldcyclohexylacetate. This esterification is typically carried out in areactor. The acetic acid and cyclohexene solution typically comprisesexcess acetic acid to minimize dimerization of the cyclohexene.Generally, the reaction is run under normal esterification conditionswhich conditions are dependent upon the reactivity of the carboxylicacid and olefin used. Using as catalyst a microcomposite of the presentinvention results in specific activity almost an order of magnitudehigher than that of other catalysts (see Table II, Example 43). Apreferred catalyst for this process is a microcomposite of the presentinvention wherein the perfluorinated ion-exchange polymer containspendant sulfonic acid groups and wherein the metal oxide is silica,alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide. Most preferred iswherein the perfluorinated ion-exchange polymer is a "NAFION®" PFIEP andthe metal oxide is silica, the most prefered "NAFION®" PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂ ═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) andhas an equivalent weight of approximately 1070.

The present invention also provides an improved process for thealkylation of an aromatic compound with an olefin wherein theimprovement comprises using the microcomposite of the present inventionas a catalyst. For example, in the alkylation of toluene with n-heptene,the toluene and heptene are dried before use and then mixed and heated,for example, to about 100° C. Dried catalyst comprising the porousmicrocomposite of the present invention is added to thetoluene/n-heptene solution and left to react. This improved process isgenerally conducted under normal alkylation conditions which conditionsare dependent upon the reactivity of the aromatic and olefin used. Ahigh rate of conversion is found using a microcomposite of the presentinvention as compared to using "NAFION®" NR 50 PFIEP as the catalyst.The preferred catalyst for this process is a microcomposite of thepresent invention wherein the perfluorinated ion-exchange polymercontains pendant sulfonic acid groups and wherein the metal oxide issilica, alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide. Most preferred iswherein the perfluorinated ion-exchange polymer is a "NAFION®" PFIEP andthe metal oxide is silica, the most preferred "NAFION®" PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂ ═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) andhas an equivalent weight of approximately 1070.

The present invention also provides an improved process for thepolymerization of tetrahydrofuran to polytetrahydrofuran. The product ispolytetramethylene ether acetate (PTMEA), the diacetate ofpolytetrahydrofuran, which can be used in the preparation of"TERATHANE®" polyether glycol (E. I. du Pont de Nemours and Company,Wilmington, Del.). A process for the polymerization of tetrahydrofurangenerally comprises contacting tetrahydrofuran with acetic anhydride andacetic acid in solution usually within a pressure reactor equipped withan agitator. The reaction can be conducted at ambient temperature. Theimprovement herein comprises adding to the solution as a catalyst theporous microcomposite of the present invention. Contact time can rangefrom 1 hr to 24 hrs.

The present invention further provides an improved process for theacylation of an aromatic compound with an acyl halide to form an arylketone. A process for the acylation of an aromatic compound generallycomprises heating the compound with the acyl halide. The improvementherein comprises contacting the aromatic compound with a catalyticporous microcomposite of the present invention. After allowingsufficient time for the reaction to complete, the aryl ketone product isrecovered.

The present invention also provides an improved process for thedimerization of an alpha substituted styrene. The improvement comprisescontacting the styrene with a catalytic porous microcomposite of thepresent invention. When using alpha methyl styrene, for example, thestyrene may be heated in solution and the catalyst added. The productcomprises a mixture of unsaturated dimers(2,4-diphenyl-4-methyl-1-pentene and 2,4-diphenyl-4-methyl-2-pentene)and saturated dimers (1,1,3-trimethyl-3-phenylidan and cis andtrans-1,3-dimethyl-1,3-diphenylcyclobutane).

A preferred catalyst for the polymerization of tetrahydrofuran, for theacylation of an aromatic compound and for the dimerization of an alphasubstituted styrene is a microcomposite of the present invention whereinthe perfluorinated ion-exchange polymer contains sulfonic acid groupsand wherein the metal oxide is silica, alumina, titania, germania,zirconia, alumino-silicate, zirconyl silicate, chromic oxide and/or ironoxide. Most preferred is wherein the PFIEP is a "NAFION®" PFIEP and themetal oxide is silica, the most preferred "NAFION®" PFIEP havingapproximately 6.3 tetrafluoroethylene (TFE) molecules for everyperfluoro perfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride)molecule (CF₂ ═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) andhas an equivalent weight of approximately 1070.

The microcomposite product of the present invention can be converted toa metal cation-exchanged material, as described by Waller (Catal. Rev.Sci. Eng. 28(1), 1-12 (1986)) for PFIEP resins. Such materials are alsouseful as catalysts.

Traditionally, olefin isomerization and alkylation with paraffins havebeen catalyzed by liquid mineral acids such as H₂ SO₄, HF or AlCl₃.Environmental concerns associated with corrosive mineral acid catalystshave encouraged process changes and the development of solid-bedcatalyst processes.

It is especially desirable to convert 1-butene to 2-butenes prior to usein the HF catalyzed alkylation process because the quality of thealkylates from 2-butenes (96-98 research octane number (RON) aresignificantly better than that from the 1-butene feed (87-89 RON).Extensive studies have been carried out on the solid acid catalyzed1-butene isomerization to 2-butenes and to isobutene. 1-Buteneisomerization to 2-butenes has been widely used as a model reaction ofcharacterizing solid acid catalysts as well. It is clear that 1-buteneisomerization to 2-butenes is not a very demanding reaction in terms ofacid strength; several of solid acid are capable of catalyzing thisisomerization involving the double bond shifting reaction. However,there remain important incentives for developing catalysts that canoperate efficiently at lower temperatures. First, competingoligomerization reactions which not only result in yield losses, butalso lead to catalyst deactivation generally become more significant athigher temperatures. Second, the equilibrium isomer distributionincreasingly favors 2-butenes at lower temperatures.

Various solid acid catalysts and even amorphous silica-alumina arecapable of catalyzing the 1-butene isomerization to 2-butenes at nearambient temperatures, but rapid deactivation is frequently encountered.Acidic cation exchange resin, sulfonic styrene-divinylbenzene copolymer("AMBERLYST 15®") was shown to be active for the 1-butene isomerizationto 2-butenes (see T. Uematsu, Bull. Chem. Soc. Japan, 1972, 45, 3329).

The present invention provides a process for the isomerization of anolefin comprising contacting said olefin at isomerization conditionswith a catalytic amount of the microcomposite of the present invention.

Olefin isomerization processes can be directed towards either skeletalisomerization, double bond isomerization or geometric isomerization.Skeletal isomerization is concerned with reorientation of the backboneof the carbon structure, for example 1-butene to isobutene. Double bondisomerization is concerned with relocation of the double bond betweencarbon atoms while maintaining the backbone of the carbon strucuture,for example 1-butene to 2-butene. Conversions between, for example cisand trans 2-pentenes, are known as geometric isomerization. The presentinvention provides primarily for double bond isomerization and includessome geometric isomerization. Skeletal isomerization is also provided toa limited degree at higher temperatures.

Preferred olefins are C₄ to C₄₀ hydrocarbons having at least one doublebond, the double bond(s) being located at a terminal end, an internalposition or at both a terminal and internal position. Most preferredolefins have 4 to 20 carbon atoms. The olefin can be straight-chained(normal) or branched and may be a primary or secondary olefin and thussubstituted with one or more groups that do not interfere with theisomerization reaction. Such substituted groups that do not interferwith the isomerization reaction could include alkyl, aryl, halide,alkoxy, esters, ethers, or thioethers. Groups that may interfere withthe process would be alcohols, carboxylic acids, amines, aldhehydes andketones. The porous microcomposite used in the present process isdescribed in detail above and comprises a perfluorinated ion-exchangepolymer containing pendant sulfonic and/or carboxylic acid groupsentrapped within and highly dispersed throughout a network of metaloxide, wherein the weight percentage of perfluorinated ion-exchangepolymer in the microcomposite is from about 0.1 to 90 percent,preferably from about 5 to about 80 percent, most preferably from about5 to about 20 percent and wherein the size of the pores in themicrocomposite is about 0.5 nm to about 75 nm.

A preferred catalyst for the present olefin isomerization process is themicrocomposite of the present invention wherein the perfluorinatedion-exchange polymer contains pendant sulfonic acid groups and whereinthe metal oxide is silica, alumina, titania, germania, zirconia,alumino-silicate, zirconyl-silicate, chromic oxide and/or iron oxide.Most preferred is wherein the perfluorinated ion-exchange polymer is a"NAFION®" PFIEP and the metal oxide is silica, the most preferred"NAFION®" PFIEP" having approximately 6.3 moles of tetrafluoroethylene(TFE) per mole of perfluoroperfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule (CF₂═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) and an equivalentweight of approximately 1070.

In another embodiment, macroporosity (pore sizes about 75 to about 1000mm) is also introduced into the microcomposite used in the presentolefin isomerization process, resulting in the microcomposite havingboth increased surface area from the micropores and mesopores (0.5-75nm) and enhanced accessibility resulting from the macropores (75-1000nm).

Contacting of the olefin with the catalyst can be effected by using thecatalyst in a fixed-bed system, a moving-bed system, a fluidized-bedsystem, or in a batch-type operation. Reactants can contact the catalystin the liquid phase, a mixed vapor-liquid phase, or a vapor phase. Thereactants can contact the catalyst in the absence of hydrogen or in thepresence of hydrogen in a molar ratio of hydrogen to olefin of fromabout 0.01 to about 10. "Absence of hydrogen" means that free ormolecular hydrogen is substantially absent in the combined reactant feedto the process. Hydrogen, if present, can be supplied totally fromoutside the isomerization process, or the outside hydrogen may besupplemented by hydrogen separated from reaction products and recycled.Inert diluents such as helium, nitrogen, argon, methane, ethane and thelike can be present either in association with hydrogen or in theabsence of hydrogen. Although the principal isomerization reaction doesnot consume hydrogen, there can be net consumption of hydrogen in sidereactions.

The isomerization of olefins is well known to be limited by thethermodynamic equilibrium of the reacting species. Isomerizationconditions for the present process comprise reaction temperaturesgenerally in the range of about 0° C. to about 300° C., preferably fromabout 25° C. to about 250° C. Pressure can range from ambient for gasphase or pressure sufficient to keep reaction in the liquid phase.Reactor operating pressures usually will range from about one atmosphereto about 100 atmospheres, preferably from about one atmosphere to about50 atmospheres. The amount of catalyst in the reactor will provide anoverall weight hourly space velocity (WHSV) of from about 0.1 to 100hr⁻¹, preferably from about 0.1 to 10 hr⁻¹ ; most preferably 0.1 to 2hr⁻¹.

Long contact time during olefin isomerization can create undesirableby-products, such as oligomers. The process of the present inventionutilizes short contact times which cuts down on the amount ofundesirable by-products. Contact times for the present process rangefrom about 0.01 hr to about 10 hrs; preferably 0.1 hr to about 5 hrs.Contact time may be reduced at higher temperatures.

The particular product-recovery scheme employed is not deemed to becritical to the present invention; any recovery scheme known in the artmay be used. Typically, the reactor effluent will be condensed and thehydrogen and inerts removed therefrom by flash separation. The condensedliquid product then is fractionated to remove light materials from theliquid product. The selected isomers may be separated from the liquidproduct by adsorption, fractionation, or extraction.

Olefin isomerization is useful in converting compounds into isomers moreuseful for particular applications. Olefins with the double bond at aterminal end tend to be more reactive and are easy to oxidize which cancause problems with their storage. Therefore, a shift to a more stableform can be desirable.

A high rate of conversion is found using the microcomposite of thepresent invention. Data in FIG. 1 shows that the microcomposite is veryefficient for the 1-butene to 2-butenes isomerization reaction undermild conditions. Even at 50° C., near thermodynamic equilibrium valuesare obtained, which at 50° C. are 4.1%, 70.5% and 25.4% for 1-butene ,trans-2-butene and cis-2-butene, respectively, and the experimental dataare 6.6%, 66.9% and 26.5%, respectively at WHSV of 1-butene of 1 hr⁻¹.The effective activation energy for 1-butene isomerization to 2-buteneswas determined to be 16.0 kcal/mol over the 13 wt % "NAFION®"PFIEP/silica microcomposite used (see Example 58). Comparisons performedin Example 57 show that "NAFION®" NR50 at 50° C. produced less than 1%conversion of the 1-butene, and at a temperature which could effectivelycatalyze the butene (200° C.) significant oligomers are also formed.

A study on the effect of temperature was carried out with a very dilutedfeed of 1-butene and at very low WHSV of 1-butene (see Table 4a, Example58). Since near equilibrium n-butene distribution was obtained at 50°C., the main interest was on the isobutene formation. However, extremelysmall amounts, well below the equilibrium concentration, of isobutenewas formed even at the highest temperature employed (250° C.). Due tothe very low WHSV of 1-butene employed (Table 4a), the oligomers formedwere quite pronounced. However, oligomers as well as isobutene formedover the microcomposite catalyst were less than that produced from the"NAFION®" NR50 beads catalyst under the same reaction conditions (seeTable 2a, Example 57), and they are both in negligible amounts at lowtemperatures (<100° C.). Even though no pronounced catalyst deactivationwas observed over more than 12 hr for the 1-butene isomerization to2-butenes, the formation of isobutene and oligomers decreased ratherrapidly at temperatures >100° C. The data listed in the Tables areobtained after about one hour on stream in all cases. These resultssuggest that isobutene could be formed through the cracking of buteneoligomers which are favored at this temperature and low WHSV or1-butene.

Overall, the extremely low surface area "NAFION®" NR50 beads result inlow activity for the 1-butene isomerization under the reactionconditions employed. However, the intrinsic isomerization activity ofthe active sites in "NAFION®" is high and when present in a moreaccessible microstructure it becomes a very effective catalyst. Veryhigh catalytic activity was observed for the 13 wt % "NAFION®"PFIEP/silica microcomposite material for which equilibrium distributionof n-butene can be readily obtained at 50° C. and is about 5-6 timesmore active than the "AMBERLYST 15®" catalyst.

The microcomposite product of the present invention is useful in a rangeof catalytic reactions as described above. For some of these reactions,some brown coloration may form upon the catalyst. Catalysts of thepresent invention can be regenerated by treatment with an acid, forexample nitric acid. The microcomposite catalyst is contacted with theacid and then stirred at a temperature ranging from about 15° C. toabout 100° C. for about 1 hr to about 26 hrs. Subsequent washing withde-ionized water is used to remove excess acid. The catalyst is thendried at a temperature ranging from about 100° C. to about 200° C.,preferably under vacuum for about 1 hr to about 60 hrs to yield theregenerated catalyst.

EXAMPLES

"NAFION®" PFIEP solutions can be purchased from Aldrich Chemical Co.,Milwaukee, Wis., or PFIEP solutions generally can be prepared using theprocedure of U.S. Pat. No. 5,094,995 and U.S. Pat. No. 4,433,082. The"NAFION®" PFIEP solution referred to in the examples below is, unlessotherwise noted, "NAFION®" NR 005, a "NAFION®" solution available fromDuPont Nafion® Products, Fayetteville, N.C., and also known as "NAFION®"SE-5110, and is prepared from resin which is approximately 6.3 (TFE)molecules for every perfluoroperfluoro(3,6-dioxa-4-methyl-7-octenesulfonyl fluoride) molecule (CF₂═CF--O--[CF₂ CF(CF₃)]--O--CF₂ CF₂ --SO₂ F (PSEPVE)) and has anequivalent weight of approximately 1070. "NAFION®" NR50 PFIEP, the sameresin used to prepared the NR005 (SE-5110) solution is available inpellet form from E. I. du Pont de Nemours and Company, Wilmington, Del.(distributed by Aldrich Chemical Company). "NAFION®" NR55 PFIEP issimilarly available and structured with carboxylic ends as well assulfonated ends on the pendant groups. "AMBERLYST 15®" sulfonated resinis a registered trademark of Rohm and Haas, Philadelphia, Pa. and issold commercially by Rohm and Haas.

Example 1 Preparation of a 40 wt % "NAFION®"/60 wt % Silica Composite

To 200 mL of a "NAFION®" perfluorinated resin solution (which consistsof 5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 25 g of a 0.4 M NaOH and the solution was stirred. Separately, inanother beaker, to 34 g of tetramethoxy silane [Si(OCH₃)₄ ] was added5.44 g of distilled water and 0.5 g of 0.04 M HCl and the solutionrapidly stirred for 10 minutes. After 10 minutes the silicon containingsolution was added to the rapidly stirring "NAFION®" solution andstirring was continued for about 10 seconds to ensure good mixing. Thesolution was left to stand. It was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 minute). Thegel was covered and left to stand for 24 hours after which time thecover was removed and the gel was placed in an oven at 90° C. with aslow stream of nitrogen flushing through the oven. The gel was left todry for 15 hours. The resultant dry glass-like pieces were then furtherdried at 140° C. under vacuum for 15 hours. The resultant material wasre-acidified with HCl as follows, to convert the perfluorosulfonic acidinto the acidic, active form. The dried material was placed in 100 mL of3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally, the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 140° C. for 24 hours. The yieldwas about 22 g. The final material was a finely particulate glass-likematerial with a light yellow coloration. The content of the "NAFION®"PFIEP was about 40 wt %. The solid had a hard texture typical of sol-gelderived silica type materials with some pieces up to a few mm in size.The material was highly porous with a surface area of 200 m² per gram(BET surface area), a single point pore volume of 0.38 cc/g and anaverage pore diameter of 5.59 nm.

Example 2 Preparation of a 40 wt % "NAFION®" PFIEP/60 wt % SilicaComposite

To 200 mL of a "NAFION®" perfluorinated resin solution (which consistsof 5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 25 g of a 0.4 M NaOH and the solution stirred. Separately, inanother beaker, to 34 g of tetramethoxy silane [Si(OCH₃)₄ ] was added5.44 g of distilled water and 0.5 g of 0.04 M HCl and the solutionrapidly stirred for 10 minutes. After 10 minutes the silicon containingsolution was added to the rapidly stirring "NAFION®" solution andstirring was continued for about 10 seconds to ensure good mixing. Thesolution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 minute). Thegel was covered and left to stand in an oven at 75° C. for 8 hours atwhich time the cover was removed and the gel was placed in an oven at90° C. with a slow stream of nitrogen flushing through the oven. The gelwas left to dry for 15 hours. The resultant dry glass-like pieces werethen further dried at 140° C. under vacuum for 15 hours. The resultantmaterial was re-acidified with HCl as follows, to convert theperfluorosulfonic acid into the acidic, active form. The dried materialwas placed in 100 mL of 3.5 M HCl and the mixture stirred for 1 hour.The HCl solution was removed via filtration and the solid resuspended in100 mL of 3.5 M HCl and stirred for a further hour. The filtering andacidification step was repeated a total of five times. Finally the solidwas placed in distilled deionized water (200 mL) and stirred for 1 hour,filtered and resuspended in water (200 mL) and stirred in order toremove the excess HCl. The solid was filtered and dried at 140° C. for24 hours. The yield was about 22 g. The final material was a glass likematerial with a light yellow coloration. The content of the "NAFION®"PFIEP was about 40 wt %. The solid had a hard texture typical of sol-gelderived silica type materials. The material was highly porous with asurface area of 131 m² per gram (BET surface area), a single point porevolume of 0.36 cc/g and an average pore diameter of 8.3 nm.

Example 3 Preparation of a 40 wt % "NAFION®" PFIEP/60 wt % SilicaComposite

To 100 mL of a "NAFION®" perfluorinated resin solution (which consistsof 5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 15 g of a 0.4 M NaOH and the solution stirred. 17 g oftetramethoxy silane was added to the rapidly stirring "NAFION®" solutionand stirring was continued for about 10 seconds to ensure good mixing.The solution was left to stand; it was observed that the whole solutionformed a gel within about a minute. The gel was covered and placed in anoven at 75° C. for 8 hours after which point the cover was removed andthe gel was placed in an oven at 75° C. with a slow stream of nitrogenflushing through the oven. The gel was left to dry for 15 hours. Theresultant dry glass-like pieces were then further dried at 140° C. underhouse vacuum for 15 hours. The resultant material was re-acidified withHCl as follows, to convert the perfluorosulfonic acid into the acidic,active form. The dried material was placed in 75 mL of 3.5 M HCl and themixture stirred for 1 hour. The HCl solution was removed via filtrationand the solid resuspended in 75 mL of 3.5 M HCl and stirred for afurther hour. The filtering and acidification step was repeated a totalof five times. Finally the solid was placed in distilled deionized water(100 mL) and stirred for 1 hour, filtered and resuspended in water (100mL) and stirred in order to remove the excess HCl. The solid wasfiltered and dried at 140° C. for 24 hours. The yield was about 11 g.The final material was a glass-like material with a light yellowcoloration. The content of the "NAFION®" PFIEP was 40 wt %. The solidhad a hard texture typical of sol-gel derived silica type materials. Thematerial is highly porous with a surface area of 134 m² per gram (BETsurface area), a single point pore volume of 0.37 cc/g and an averagepore diameter of 8.2 nm.

Example 4 Preparation of a 40 wt % "NAFION®" PFIEP/60 wt % SilicaComposite

To 200 mL of a "NAFION®" perfluorinated resin solution (which consistsof 5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 17 g of a 0.4 M NaOH and the solution stirred. Separately, inanother beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄ ] was added5.44 g of distilled water and 0.5 g of 0.04 M HCl and the solutionrapidly stirred for 10 minutes. After 10 minutes the silicon containingsolution was added to the rapidly stirring "NAFION®" solution andstirring was continued for about 10 seconds to ensure good mixing. Thesolution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 2 min). The gelwas covered and left to stand for 24 hours after which point the coverwas removed and the gel was placed in an oven at 90° C. with a slowstream of nitrogen flushing through the oven. The gel was left to dryfor 15 hours. The resultant dry glass-like pieces were then furtherdried at 140° C. under house vacuum for 15 hours. The resultant materialwas reacidified with HCl as follows, to convert the perfluorosulfonicacid into the acidic, active form. The dried material was placed in 100mL of 3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 140° C. for 24 hours. The yieldwas about 22 g. The final material was a glass-like material with alight yellow coloration. The content of the "NAFION®" PFIEP was 40 wt %.The solid had a hard texture typical of sol-gel derived silica typematerials with some pieces up to a few mm in size. The material washighly porous with a surface area of 294 m² per gram (BET surface area),a single point pore volume of 0.30 cc/g and an average pore diameter of3.5 nm.

Example 5 Preparation of a ca. 20 wt % "NAFION®" PFIEP/80 wt % SilicaComposite

To 100 mL of a "NAFION®" perfluorinated resin solution (which consistsof 5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 25 g of a 0.4 M NaOH and the solution stirred. Separately, inanother beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄ ] was added5.44 g of distilled water and 0.5 g of 0.04 M HCl and the solutionrapidly stirred for 10 minutes. After 10 minutes the silicon containingsolution was added to the rapidly stirring "NAFION®" solution andstirring was continued for about 10 seconds to ensure good mixing. Thesolution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 min). The gelwas covered and left to stand for 24 hours after which point the coverwas removed and the gel was placed in an oven at 90° C. with a slowstream of nitrogen flushing through the oven. The gel was left to dryfor 15 hours. The resultant dry glass-like pieces were then furtherdried at 140° C. under house vacuum for 15 hours. The resultant materialwas reacidified with HCl as follows, to convert the perfluorosulfonicacid into the acidic, active form. The dried material was placed in 100mL of 3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 125° C. for 24 hours. The finalmaterial was a glass-like material with a light yellow coloration. Thecontent of the "NAFION®" PFIEP was about 20 wt %. The solid had a hardtexture typical of sol-gel derived silica type materials. The materialwas highly porous with a surface area of 287 m² per gram (BET surfacearea), a single point pore volume of 0.63 cc/g and an average porediameter of 6.70 nm.

Example 6 Preparation of a ca. 10 wt % "NAFION®"/90 wt % SilicaComposite

To 50 mL of a "NAFION®" perfluorinated resin solution (which consists of5 wt % "NAFION®" PFIEP in a mixture of lower alcohols and water) wasadded 25 g of a 0.4 M NaOH and the solution stirred. Separately, inanother beaker to 34 g of tetramethoxy silane [Si(OCH₃)₄ ] was added5.44 g of distilled water and 0.5 g of 0.04 M HCl and the solutionrapidly stirred for 10 minutes. After 10 minutes the silicon containingsolution was added to the rapidly stirring "NAFION®" solution andstirring was continued for about 10 seconds to ensure good mixing. Thesolution was left to stand; it was observed that the whole solutionformed a gel within a few seconds (typically 15 sec to 1 min). The gelwas covered and left to stand for 24 hours after which point the coverwas removed and the gel was placed in an oven at 90° C. with a slowstream of nitrogen flushing through the oven. The gel was left to dryfor 15 hours. The resultant dry glass-like pieces were then furtherdried at 140° C. under house vacuum for 15 hours. The resultant materialwas reacidified with HCl as follows, to convert the perfluorosulfonicacid into the acidic, active form. The dried material was placed in 100mL of 3.5 M HCl and the mixture stirred for 1 hour. The HCl solution wasremoved via filtration and the solid resuspended in 100 mL of 3.5 M HCland stirred for a further hour. The filtering and acidification step wasrepeated a total of five times. Finally the solid was placed indistilled deionized water (200 mL) and stirred for 1 hour, filtered andresuspended in water (200 mL) and stirred in order to remove the excessHCl. The solid was filtered and dried at 125° C for 24 hours. The finalmaterial was a glass like material with a light yellow coloration. Thecontent of the "NAFION®" PFIEP was about 10 wt %. The solid had a hardtexture typical of sol-gel derived silica type materials. The materialwas highly porous with a surface area of 270 m² per gram (BET surfacearea), a single point pore volume of 0.59 cc/g and an average porediameter of 6.50 nm.

Example 7 Preparation of "NAFION®" PFIEP 40 wt % and Silica 60 wt % withDual Porosity having Both Large (ca. 500 nm) and Small (ca. 2-15 nm)Pores

To 100 mL of the "NAFION®" solution(which consists of 5 wt % "NAFION®"PFIEP in a mixture of lower alcohols and water) was added 15 g of a 0.4M NaOH and the solution stirred. 4 g of calcium carbonate (AlbafilSpecialty Minerals, Adams, Mass. with a particle size of about 0.5microns) was added to the basic "NAFION®" and calcium carbonate mixturewhich was ultrasonicated for 1 minute to 10 minutes using a sonic probe(Heat Systems Inc., Farmingdale, N.Y.). Separately, in another beaker to17 g of tetramethoxy silane [Si(OCH₃)₄ ] was added 2.7 g of distilledwater and 0.25 g of 0.04 M HCl and the solution rapidly stirred for 10minutes. After 10 minutes the silicon containing solution was added tothe rapidly stirring "NAFION®" solution and stirring was continued forabout 10 seconds to ensure good mixing. The solution was left to stand;it was observed that the whole solution formed a gel within a fewseconds (typically 10 sec to 1 min). The gel was covered and left tostand for 4 hours after which point the cover was removed and the gelwas placed in an oven at 90° C. with a slow stream of nitrogen flushingthrough the oven. The gel was left to dry for 15 hours. The resultantdry glass-like pieces were then further dried at 140° C. under housevacuum for 15 hours. The resultant material was reacidified with HCl asfollows, to convert the perfluorosulfonic acid into the acidic, activeform and also to dissolve out the calcium carbonate. The dried materialwas placed in 100 mL of 3.5 M HCl and the mixture stirred for 1 hour.Upon addition of the acid a large amount of gas was evolved (due to thereaction of the acid with HCl). The HCl solution was removed viafiltration and the solid resuspended in 100 mL of 3.5 M HCl and stirredfor a further hour. The filtering and acidification step was repeated atotal of five times. Finally the solid was placed in distilled deionizedwater (200 mL) and stirred for 1 hour, filtered and resuspended in water(200 mL) and stirred in order to remove the excess HCl. The solid wasfiltered and dried at 125° C. for 24 hours. The final material was aglass-like material with a light yellow coloration. The microstructureof the derived material was investigated using scanning electronmicroscopy. The micrograph clearly shows very large pores about 0.5-1micron in size. Also using energy dispersive x-ray analysis, no Ca couldbe detected showing that most of the calcium carbonate has been removedupon reacidification. The material was highly porous with a surface areaof 310 m² per gram (BET surface area), and a single point pore volume of0.46 cc/g.

Example 8 Catalytic testing of "NAFION®" PFIEP/Silica Composites usingthe Alkylation of Toluene with n-heptene

It is well known in the art that solid acid catalysts can catalyze arange of reactions, for example, alkylation reactions. We describe theuse of the silica/"NAFION®" PFIEP composites to catalyze the alkylationof toluene with n-heptene, and measure the conversion of heptene andtoluene using gas chromatography.

As a comparison we also tested the catalytic activity of the "NAFION®"PFIEP itself which is available in pellet form from E. I. du Pont deNemours and Company, Wilmington, Del. 19898 (distributed by AldrichChemical Company) and is known as "NAFION®" NR 50 PFIEP.

A typical reaction is described as follows.

Both toluene and heptene were dried over 3A molecular sieve before use(dried for 24-hours). In a round bottom flask was added 15.6 g oftoluene and 8.4 g of n-heptene, and a "TEFLON®" coated magnetic stirreradded. A reflux condenser was attached to the flask and a slow stream ofnitrogen passed over the top of the reflux condenser to minimizemoisture. The flask and contents were heated to 100° C. A sample of 1gram of the "NAFION®" PFIEP/silica catalyst (which is made up of 40 wt %"NAFION®" PFIEP and 60 wt % silica) as described in Example 1 was gentlyground to break down the large pieces (to give a material about 0.1 to 1mm in size) and the solid dried in vacuum at 140° C. for 24 hours. Thedried material was added to the toluene/n-heptene mixture and thesolution stirred and left to react for exactly 2 hours. After 2 hours asample was removed and the conversion of heptene was measured using gaschromatography. In the GC analysis dodecane was used as a standard. Theconversion of heptene was measured to be 90% to 95%, leaving only 10% to5% of the heptene unreacted.

As a comparison experiment, the catalytic activity of 0.4 g of "NAFION®"NR 50 PFIEP was tested. 0.4 g represents the same weight of "NAFION®"PFIEP as tested above for the composite. The exact same procedure wasused, drying the "NAFION®" NR 50 PFIEP at 140° C. for 24 hours andadding the "NAFION®" NR 50 PFIEP to the stirred solution of toluene(15.6 g) and heptene (8.4 g) at 100° C. After 2 hour reaction time theconversion was found to be about 3%, leaving 97% of the hepteneunreacted.

Example 9

The procedure as described in Example 7 was carried out exactly exceptin this case a 20 wt % "NAFION®" PFIEP/80 wt % silica composite wasevaluated for catalytic activity, prepared as described in Example 4.Using 1 g of catalyst (and 15.6 g toluene and 8.4 heptene) lead to aconversion of heptene of 79%. As a comparison, using 0.2 g of NR 50 leadto a conversion of between 1-2%.

Example 10

The procedure as described in Example 7 was carried out exactly exceptin this case a 10 wt % "NAFION®" PFIEP/90 wt % silica composite wasevaluated for catalytic activity, prepared as described in Example 5.Using 1 g of catalyst (and 15.6 g toluene and 8.4 heptene) lead to aconversion of heptene of 75%. As a comparison, using an equivalentweight of 0.1 g of NR 50 lead to a conversion of less than 1% leavingmore than 99% of the heptene unreacted.

Example 11 Preparation of a 40 wt % "NAFION®" PFIEP/60 wt % SilicaComposite using Sodium Silicate as the Silica Source

150 mL of a 9% sodium silicate solution, which was made up by taking45.6 mL of a sodium silicate solution (which contained 29.6% of silica)in SiO₂ and adding sufficient distilled water to bring the volume up to150 mL. The measured pH was about 12.5. The solution was cooled to about10° C. using an ice bath. The solution was stirred and an DOWEX® cationexchange resin was added until the pH reached 2.5, over about 2-3minutes. This process generated polysilicic acid. The solution wasseparated from the resin by filtration. 35 mL of a 5% "NAFION®" PFIEP inalcohol/water mixture was added to the above solution with rapidstirring and the stirrer was stopped after about 1 min. The solution wascovered and placed in an oven for 17 h at 90° C., after which point thewhole system formed a solid gel. The cover was removed and the materialwas dried in an oven at 90° C. for 24 hours, and finally dried undervacuum at 140° C. for 17 h. This yielded hard, glass like pieces, whichare typical of silica gel, with sizes in the range of about 0.1 to 5 mm.The dried glass was reacidified in 3.5 M HCl (ca. 100 mL of acid), andwas stirred and filtered and the process repeated five times. Finallythe material was washed by stirring with water (100 mL) and filteringand repeating the process 2 times. The reacidified material was dried at140° C. for 17 h, which yielded a glass like, slightly brown, "NAFION®"PFIEP/silica composite.

Catalytic Testing

Both toluene and n-heptene were dried over 3A molecular sieve before use(dried for 24 hours). In a round bottom flask was added 15.6 g oftoluene and 8.4 g of n-heptene, and a "TEFLON®" coated magnetic stirreradded. A reflux condenser was attached to the flask and a slow stream ofnitrogen passed over the top of the reflux condenser to minimizemoisture. The flask and contents were heated to 100° C. A sample of 1gram of the "NAFION®" PFIEP/silica catalyst (which was made up of 10 wt% "NAFION®" PFIEP and 90 wt % silica) as described above was gentlyground to break down the large pieces (to give a material about 0.1 to 1mm in size) and the solid dried in vacuum at 140° C. for 24 hours. Thedried material was added to the toluene/n-heptene mixture and thesolution stirred and left to react for exactly 2 hours at 100° C. After2 hours a sample was removed and the conversion of n-heptene wasmeasured using gas chromatography. In the GC analysis dodecane was usedas a standard. The conversion of heptene was measured to be 36%.

Example 12 Preparation of a 20 wt % "NAFION®38 PFIEP/80 wt % AluminaComposite

49.2 g of aluminum tri-secbutoxide [Al(OC₄ H₉)₃ ] was added to 362 mL ofdistilled water at 75° C. and the mixture was left to stir for 15 min.To the stirred solution was added 1.36 g of a 69% concentrated nitricacid solution and the material was transfered to a sealed jar, and leftin an oven at 90° C. for 24 h. A free flowing aluminum containingsolution resulted. The formation of alumina gels that form poroustransparent alumina has been described by B. E. Yoldas, in J. Mat. Sci10 (1975) 1856 and B. E. Yoldas, Ceramics Bulletin, 54 (1975) 289. To200 mL of the above solution was added 20 mL of a 5% "NAFION®" PFIEPcontaining alcohol/water resin solution. The material was stirred on ahot plate with a solution temperature of 80° C. until all of the solventevaporated, leaving a glass-like solid. The glass-like solid hadparticles in the range of about 0.1 to 2 mm. The material containedabout 20 wt % "NAFION®" PFIEP and 80 wt % alumina. The material wasreacidified with 4M HCl in dioxane.

Example 13 13.5 wt. % "NAFION®" PFIEP in Silica, with Pore Diameter ca.10 nm

204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3 g of0.04M HCl was stirred for 45 mins. to give a clear solution. To 300 mLof a "NAFION®" solution (which contains 5% of "NAFION®" PFIEP by weight)was added 150 mL of a 0.4M NaOH solution, while the "NAFION®" solutionwas being stirred. After addition of the sodium hydroxide solution theresulting solution was stirred for a further 15 min. The siliconcontaining solution, prepared as described above, was added rapidly tothe stirred "NAFION®" containing solution. After about 10-15 seconds thesolution gelled to a solid mass. The gel was placed in an oven and driedat a temperature of about 95° C., over a period of about 2 days,followed by drying under vacuum overnight. The hard glass-like productwas ground and passed through a 10-mesh screen. The material was thenstirred with 3.5M HCl for 1 hour (with 500 mL of acid), followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 hours. Yield of dried product was 98 g. The surface area(determined by BET), pore volume and pore diameter was determined to be344 m² /g, 0.85 cc/g and 9.8 nm, respectively.

Example 14 40 wt. % "NAFION®" PFIEP in Silica, with Pore Diameter ca. 10nm

204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3 g of0.04M HCl was stirred for 45 mins. to give a clear solution. To 1200 mLof a "NAFION®" solution (which contains 5% of "NAFION®" PFIEP by weight)was added 150 ml of a 0.4M NaOH solution, while the "NAFION®" solutionwas being stirred. After addition of the sodium hydroxide solution, theresulting solution was stirred for a further 15 min. The siliconcontaining solution, prepared as described above, was added rapidly tothe stirred "NAFION®" containing solution. After about 10-15 seconds thesolution gelled to a solid mass. The gel was placed in an oven and driedat a temperature of about 95° C., over a period of about 2 days,followed by drying under vacuum overnight. The hard glass-like productwas ground and passed through a 10-mesh screen. The material was thenstirred with 3.5M HCl for 1 hour (with 500 mL of acid) followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h. Yield of dried product was 130 g. The surface area(determined by BET), pore volume and pore diameter was determined to be468 m² /g, 1.05 cc/g and 8.9 nm, respectively.

Example 15 8 wt. % "NAFION®" PFIEP in Silica, with Pore Diameter ca. 10nm

204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3 g of0.04M HCl was stirred for 45 mins. to give a clear solution. To 150 mLof a "NAFION®" solution (which contains 5% of "NAFION®" PFIEP by weight)was added 150 mL of a 0.4M NaOH solution, while the "NAFION®" solutionwas being stirred. The sodium hydroxide was added over about 1 min.After addition of the sodium hydroxide solution, the resulting solutionwas stirred for a further 15 min. The silicon containing solution,prepared as described above, was added rapidly to the stirred "NAFION®"containing solution. After about 10-15 seconds the solution gelled to asolid mass. The gel was placed in an oven and dried at a temperature ofabout 95° C., over a period of about 2 days, followed by drying undervacuum overnight. The hard glass-like product was ground and passedthrough a 10-mesh screen. The material was then stirred with 3.5M HClfor 1 hour (with 500 mL of acid), followed by washing with 500 mL ofdeionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Yieldof dried product was 82 g. The surface area (determined by BET), porevolume and pore diameter was determined to be 412 m² /g, 0.84 cc/g and10.3 mn, respectively.

Example 16 13 wt. % "NAFION®" PFIEP in Silica, with Pore Diameter ca. 20nm

204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3 g of0.04M HCl was stirred for 45 mins. to give a clear solution. To 300 mLof a "NAFION®" solution (which contains 5% of "NAFION®" PFIEP by weight)was added 150 mL of a 0.8M NaOH solution, while the "NAFION®" solutionwas being stirred. After addition of the sodium hydroxide solution theresulting solution was stirred for a further 15 min. Both the siliconcontaining solution and the "NAFION®" containing solution were cooled inice to lower the solution temperature to about 10° C. The siliconcontaining solution, prepared as described above, was added rapidly tothe stirred "NAFION®" containing solution. After about 10 seconds thesolution gelled to a solid mass. The gel was placed in an oven and driedat a temperature of about 90° C., over a period of about 2 days,followed by drying under vacuum overnight. The hard glass-like productwas ground and passed through a 10-mesh screen. The material was thenstirred with 3.5M HCl for 1 hour (with 500 mL of acid) followed bywashing with 500 mL of deionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h. Yield of dried product was 97 g. The surface area(determined by BET), pore volume and pore diameter was determined to be123 m² /g, 0.84 cc/g and 22 nm, respectively.

Example 17 40 wt. % "NAFION®" PFIEP in Silica, with both Small ca. 10 nmand Large ca. 0.5 μm Sized Pores, Dual Porosity Gels

255 g of tetramethoxysilane (TMOS), 40.75 g of distilled water and 3.75g of 0.04M HCl was stirred for 45 mins. to give a clear solution. To1500 mL of a "NAFION®" solution (which contains 5% of "NAFION®" PFIEP byweight) was added 187 mL of a 0.4M NaOH solution, while the Nafionsolution was being stirred, followed by 187 g of calcium carbonate(supplied by Albafil Specialty Minerals). After addition of the sodiumhydroxide solution, the resulting solution was sonicated for a further15 min. using a Branson ultrasonic probe to ensure dispersion of thecalcium carbonate. The silicon containing solution, prepared asdescribed above, was added rapidly to the stirred "NAFION®" containingsolution. After about 10-15 seconds the solution gelled to a solid mass.The gel was placed in an oven and dried at a temperature of about 95°C., over a period of about 2 days, followed by drying under vacuumovernight. The hard glass-like product was ground and passed through a10-mesh screen. The material was then stirred with 3.5M HCl for 1 hour(with 500 mL of acid), followed by washing with 500 mL of deionizedwater. The solid was collected by filtration. Acidification, washing,and filtration were repeated a total of 5 times and after the final washthe solid was dried under vacuum at 100° C. for 24 h. Yield of driedproduct was 168 g. The surface area (determined by BET), pore volume andpore diameter was determined to be 57 m² /g, 0.21 cc/g and 13 nm,respectively.

Example 18 13 wt. % "NAFION®" PFIEP in Silica, with Pore Diameter ca.2.1 nm

204 g of tetramethoxysilane (TMOS), 33 g of distilled water and 3 g of0.04M HCl was stirred for 30 mins. to give a clear solution. To 300 mLof a "NAFION®" solution, HCl was added to yield an HCl concentration of0.01M. The silicon containing solution, prepared as described above, wasadded rapidly to the stirred "NAFION®" containing solution. The vesselwas sealed and placed in a heated oven overnight at 65° C., after whichpoint the system gelled. The top was removed and the flask and contentswere placed in an oven and dried at a temperature of about 95° C., overa period of about 2 days, followed by drying under vacuum overnight. Thehard glass-like product was ground and passed through a 10-mesh screen.The material was then stirred with 3.5M HCl for 1 hour (with 500 mL ofacid), followed by washing with 500 mL of de-ionized water. The solidwas collected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24 h. Yield of dried product was 96 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 563 m² /g, 0.15 cc/g and 2.1 nm, respectively.

Example 19 42 wt. % "NAFION®" PFIEP in Silica, No Acid Hydrolysis Stepvia TMOS

15 g of 0.4M NaOH was added to 100 mL of a 5% "NAFION®" solution. Tothis solution was added 17 g of TMOS and the solution gelled within 15secs. The solid gel was dried at 95° C. in an oven vented with flowingnitrogen, for 2 days, followed by vacuum drying at 140° C. The solid wasre-acidified with 3.5M HCl for 1 hour (with 50 mL of acid), followed bywashing with 50 mL of de-ionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24h. Yield of dried product was 9 g. The surface area(determined by BET), pore volume and pore diameter was determined to be330 m² /g, 0.36 cc/g and 8.3 nm, respectively.

Example 20 8 wt. % "NAFION®" in Silica, adding Silica to "NAFION®", thenthe NaOH

20.4 g of TMOS, 3.2 g of water and 0.2 g of 0.04M HCl was stirred for 30min. and added to 15 mL of 5% "NAFION®" solution with rapid stirring. Tothe silica and "NAFION®" containing solution, 15 g of 0.4M NaOH wasrapidly added while the solution was rapidly stirred. The solutionturned to a solid gel within about 10 seconds. The gel was dried at 98°C. for 2 days followed by drying under vacuum overnight at 100° C. Thesolid was re-acidified with 3.5M HCl for 1 hour (with 150 mL of acid),followed by washing with 50 mL of de-ionized water. The solid wascollected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24h. Yield of dried product was 9 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 364 m² /g, 1.06 cc/g and 11.5 nm, respectively.

Example 21 "NAFION®" PFIEP/Silica Composite via Tetraethoxysilane

108 g of tetraethoxysilane, 28.8 g of water and 2.4 g of 0.04M HCl wasstirred for 2.5 hours to give a clear solution. 55 mL of 0.4M NaOH wasadded to 75 mL of stirred "NAFION®" solution (5%) and the stirringcontinued for 15 mins. The silica solution was rapidly added to thestirring "NAFION®" solution and the system formed a gel within 10-15seconds. The gel was dried at 95° C. for two days followed by vacuumdrying at 125° C. overnight. The gel was ground and passed through a10-mesh screen and re-acidified with 3.5M HCl for 1 hour (with 250 mL ofacid), followed by washing with 250 mL of de-ionized water. The solidwas collected by filtration. Acidification, washing and filtration wererepeated a total of 5 times and after the final wash the solid was driedunder vacuum at 100° C. for 24 h. Yield of dried product was 32 g. Thesurface area (determined by BET), pore volume and pore diameter wasdetermined to be 330 m² /g, 0.75 cc/g and 7.5 nm, respectively.

Example 22 "NAFION®" PFIEP/Silica Composite via Sodium Silicate Solution

To 100 g of sodium silicate solution (which contained 29% by weight ofsilica), was added 210 mL of water. To this solution 300 g of DOWEX®cation exchange resin was very quickly added and stirred rapidly untilthe pH dropped to about 3 (in less than 2 minutes). The solution wasfiltered. 30 mL of a 5% "NAFION®" solution was added to 150 mL of thefiltrate while it was stirred. 5 mL of 2M NaOH was then added and thesolution gelled; pH was close to 6.0. The gel was dried at 95° C. fortwo days and then dried under vacuum at 100° C. for 1 day. The gel wasground and passed through a 10-mesh screen and re-acidified with 3.5MHCl for 1 hour (with 250 mL of acid), followed by washing with 250 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times and after thefinal wash the solid was dried under vacuum at 100° C. for 24h. Yield ofdried product was 15.6 g. The surface area (determined by BET), porevolume and pore diameter was determined to be 350 m² /g, 0.74 cc/g and7.1 nm, respectively.

Example 23 6 wt. % "NAFION®" PFIEP in Silica, using Sodium SilicateSolution

50 g of distilled water was added to 20 g of a sodium silicate solution(which contained 29% by weight of silica). 10 g of a 5% "NAFION®"solution was added with rapid stirring. The solution was added dropwiseover about 10 mins. Next, 24 mL of a 12.41% HCl solution was added whilerapidly stirring, and the pH dropped to 1.8. Next, 0.4M NaOH was addedrapidly to adjust the pH to 6, after which point the solution formed agel. The gel was ground and passed through a 10-mesh screen andre-acidified with 3.5M HCl for 1 hour (with 100 mL of acid), followed bywashing with 100 mL of de-ionized water. The solid was collected byfiltration. Acidification, washing and filtration were repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24h. Yield of dried product was 6.5 g. The surface area(determined by BET), pore volume and pore diameter was determined to be387 m² /g, 0.81 cc/g and 7.1 nm, respectively.

Example 24 10 wt. % "NAFION®" PFIEP in Silica via "LUDOX®" 40 ColloidalSilica

200 mL of "LUDOX®" 40 (which contains 80 g of silica) was added to 160mL of 5% "NAFION®" solution. The pH was adjusted to 6.0 using 3.5M HCl.The solution was placed in a sealed glass vessel and placed in an ovenat 60-70° C. After 1 hour the system gelled. The material was dried at90° C., followed by vacuum drying at 140° C. The gel was reacidifiedwith 3.5M HCl for 1 hour (with 500 mL of acid), followed by washing with500 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h.

Example 25 A Composite of "NAFION®" (NR55) PFIEP in Silica

150 mL of a 5% solution of "NAFION®" (NR55, which contains both sulfonicacid and carboxylic acid groups), was added to 60 mL of isopropanol, 15mL of methanol, and 75 mL of water. To this was added 150 g of 0.4MNaOH. Separately, 204 g of TMOS, 32.6 g of water and 3 g of 0.04M HClwas stirred for 20 mins and then added to the NR55 solution. The gelthat formed was dried at 100° C. over 24 hrs, ground and passed througha 10-mesh screen. The material was then stirred with 3.5M HCl for 1 hour(with 500 mL of acid), followed by washing with 500 ml of de-ionizedwater. The solid was collected by filtration. Acidification, washing andfiltration were repeated a total of 5 times and after the final wash thesolid was dried under vacuum at 100° C. for 24 h. Yield of dried productwas 92.6 g. The "NAFION®" PFIEP content was 7.5 wt %.

Example 26 "NAFION®" PFIEP Entrapped in Si--Al--Zr Composite

20.4 g of TMOS, 3.6 g of water and 0.3 g of 0.04M HCl was stirred for 20mins. and added to 5 g of the mixed aluminum/zirconium complex (Al₂Zr(OR)_(x) available from Gelest, Tullytown, Pa. The mixture was stirredfor 5 mins. 30 g of 5% "NAFION®" solution and 15 g of 0.4M NaOH weremixed and added to the Si--Al--Zr containing solution, and the materialwas placed in an oven at 75° C. and dried at 100° C.

Example 27 Nitric Acid Treatment of Used or Organic ContaminatedComposites

The above described materials of the present invention are used for arange of catalytic reactions. For some reactions, some brown colorationmay form upon the catalyst. Catalysts can be regenerated by treatmentwith acid. 100 g of 13 wt. % "NAFION®" PFIEP in silica was mixed with 1liter of 35% nitric acid and the solid stirred at 75° C. overnight. Thewhite solid obtained was washed with de-ionized water to remove excessacid and was dried at 100° C. under vacuum overnight.

Example 28 Catalytic Testing of "NAFION®" PFIEP/Silica Composites Usingthe Alkylation of Toluene with n-heptene

It is well known in the art that solid acid catalysts can catalyze arange of reactions, for example, alkylation reactions. Thesilica/"NAFION®" PFIEP composites of the present invention can be usedto catalyze the alkylation of toluene with n-heptene, measuring theconversion of n-heptene using gas chromatography.

As a comparison, the catalytic activity of "NAFION®" PFIEP itself whichis available in pellet form from E. I. du Pont de Nemours and Company,Wilmington, Del., and is known as "NAFION®" NR 50, was also tested.

ILLUSTRATIVE EXAMPLE OF PRESENT INVENTION

Both toluene and n-heptene were dried over 3A molecular sieve before use(dried for 24 hours). In a round bottom flask was added 15.6 g oftoluene and 8.4 g of n-heptene, and a Teflon coated magnetic stirreradded. A reflux condenser was attached to the flask and a slow stream ofnitrogen passed over the top of the reflux condenser to minimizemoisture. The flask and contents were heated to 100° C. A sample of 1 gof the "NAFION®" PFIEP/silica catalyst as described in Example 14 wasdried in vacuum at 150° C. for 15 hours. The dried material was added tothe toluene/n-heptene mixture and the solution stirred and left to reactfor exactly 2 hours. After two hours a sample was removed and theconversion of n-heptene was measured using gas chromatography. In the GCanalysis dodecane was used as a standard. The conversion of n-heptenewas measured to be 98%, leaving only 2% of the heptene unreacted.

COMPARATIVE EXAMPLE

As a comparison experiment, the catalytic activity of 0.4 g of "NAFION®"NR50 PFIEP was tested. 0.4 g represents the same weight of "NAFION®"PFIEP as tested above for the composite of the present invention. Theexact same procedure was used, drying the NR50 at 150° C. for 24 hoursand adding the NR50 to the stirred solution of toluene (15.6 g) andheptene (8.4 g) at 100° C. After 2 hour reaction time the conversion wasfound to be about 3%, leaving 97% of the heptene unreacted.

Example 29

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 13 was used in thecatalysis run. Thus, 1 g of a 13 wt. % Nafion in silica was used. Theconversion was found to be 89% of heptene.

As a comparative example, 0.13 g of "NAFION®" NR50 was used as catalyst(again with the same conditions as described in Example 28, comparativeexample). The measured conversion was about 1% of heptene.

Example 30

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 15 was used in thecatalysis run. The conversion was found to be 84% of heptene.

Example 31

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 16 was used in thecatalysis run. The conversion was found to be 94% of heptene.

Example 32

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 17 was used in thecatalysis run. The conversion was found to be 97% of heptene.

Example 33

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 18 was used in thecatalysis run. The conversion was found to be 91% of heptene.

Example 34

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 19 was used in thecatalysis run. The conversion was found to be 83% of heptene.

Example 35

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 20 was used in thecatalysis run. The conversion was found to be 93% of heptene.

Example 36

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 21 was used in thecatalysis run. The conversion was found to be 86% of heptene.

Example 37

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 22 was used in thecatalysis run. The conversion was found to be 82% of heptene.

Example 38

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 23 was used in thecatalysis run. The conversion was found to be 76% of heptene.

Example 39

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 24 was used in thecatalysis run. The conversion was found at to be 28% of heptene.

Example 40

The illustrative example as described in Example 28 was carried out withthe exception that 1 g of the material from Example 25 was used in thecatalysis run. The conversion was found to be 64% of heptene.

Example 41 Catalytic Testing of "NAFION®" PFIEP/Silica Composite Usingthe Dimerization of Alpha Methylstyrene (AMS)

The dimerization of alpha-methylstyrene (AMS) with "NAFION®" PFIEP hasbeen studied in detail in the past (B. Chaudhuri and M. M. Sharme, Ind.Eng. Chem. Res. 1989, 28, 1757-1763). The products of the reaction are amixture of the individual unsaturated dimers(2,4-diphenyl4-methyl-1-pentene and 2,4-diphenyl-4-methyl-2-pentene) andthe saturated dimers (1,1,3-trimethyl-3-phenylindan and cis andtrans-1,3-dimethyl-1,3-diphenylcyclobutane). With "NAFION®" PFIEP as thecatalyst, the reaction was found to be very slow.

ILLUSTRATIVE EXAMPLE OF THE PRESENT INVENTION

0.5 g of the solid made via Example 13 was used as catalyst. 5 g ofalphamethylstyrene and 45 g of cumene as solvent was heated to 60° C. Tothis solution 0.5 g of the catalyst was added, and reagents and catalystwere stirred and heated at 60° C. After 30 mins. the amount ofalphamethylstyrene was measured using GC analysis, which showed aconversion of about 99%, with less than 1% of the reactant AMSremaining. After 200 mins. of reaction time the conversion of AMS wasabout 100%.

COMPARATIVE EXAMPLE

0.07 g of 100% "NAFION®" NR50 PFIEP was used as catalyst. 5 g ofalphamethylstyrene and 45 g of cumene as solvent were heated to 60° C.To this solution 0.07 g of the catalyst was added, and reagents andcatalyst were stirred and heated at 60° C. After 30 mins. the amount ofalphamethylstyrene was measured using GC analysis, which showed aconversion of less than 1%, with ore than 99% of the reactant AMSremaining. After 200 mins. of reaction time the conversion ofalphamethylstyrene was about 5%, with 95% of the AMS unchanged.

Example 42 Catalytic Testing of NAFION®" PFIEP/Silica Composite Usingthe Nitration of Benzene to Form Nitrobenzene

A 250 mL three necked flask was equipped with a Dean-Stark moisture trapand a magnetic stirrer. The flask was loaded with 70-75 g benzene, 10 gMgSO₄ (as a desiccant), 5.0 g 1,3,5-trichlorobenzene (internal standard)and 7.5 g of the appropriate acid catalyst. The mixture was heated toreflux at atmospheric pressure, under inert atmosphere. After about 30min. at reflux, a feed pump was turned on, and 90% HNO₃ was fed into thereactor at a rate of about 0.06 mL/min. The reaction mixture wasmaintained at reflux, and samples were removed at 15-30 minute intervalsfor GC analysis. The average nitric acid conversions and nitrobenzeneselectivities, over the 150 min. run time are given below in Table I:

                  TABLE I                                                         ______________________________________                                                            % HNO.sub.3                                                                             % Selectivity                                     Acid Catalyst Conversion (nitrobenzene)                                     ______________________________________                                        13.5% "NAFION ®"/silica composite                                                             82 ± 8 99.6 ± 0.2                                     (from Example 13)                                                             "NAFION ®" NR50 beads 64 ± 8 98.8 ± 1.0                             None 35 ± 7 97.9 ± 0.6                                                ______________________________________                                    

Example 43 Catalytic Testing of "NAFION®" PFIEP/Silica Composite Usingthe Conversion of Cyclohexene with Acetic Acid to Cyclohexl Acetate

The esterification of cyclohexene with acetic acid using solid acidcatalyst was carried out in liquid phase in a Fisher-Porter reactor. Thereactor comprised of a glass tube fitted with a gas injection port,liquid sampling port, thermocouple, and pressure gauge. Mixing in thereactor was provided by a magnetic stirrer and the reactor was heatedwith a hot air gun. The glass reactor was operated in the batch modewith acetic acid, cyclohexene, cyclooctane (internal standard), and thecatalyst loaded into the reactor before the reactor was pressurized andheated to the desired operating condition. The reactants and productswere analyzed by gas chromatograph-mass spectrometer.

The reaction was performed in excess of acetic acid (aceticacid/cyclohexene molar ratio of 5:1) to minimize the dimerization ofcyclohexene. Four different catalysts were tested at a temperature andpressure of 100° C. and 50 psig, respectively, for 5 hours time onstream. A blank run was also carried out under identical operatingconditions to determine whether the reaction proceeds in the absence ofany catalyst. Little or no cyclohexyl acetate was formed in the absenceof catalyst under the operating conditions mentioned above.

The four catalysts tested in this series of experiments includedsulfated zirconia, Amberlyst 15 (Rohm and Haas), "NAFION®" NR50(DuPont), and 13.5% "NAFION®" PFIEP/silica microcomposite material ofthe present invention (Example 13). The efficiency of the catalystsafter 5 hours time on stream were compared on the basis of specificactivity of the catalysts (measured as gmol of cyclohexylacetate/g-cat.hr) for the esterification reaction. The specific activityof the catalysts have been reported in Table II.

                  TABLE II                                                        ______________________________________                                                         Specific Activity × 10.sup.2                              (gmol cyclohexyl acetate)                                                    Catalyst (gm catalyst) · (hr)                                      ______________________________________                                        Sulfated Zirconia                                                                              16.8                                                           Amberlyst 15 82.4                                                             "NAFION ®" NR50 86.3                                                      13.5% "NAFION ®" 677.5                                                    PFIEP/silica                                                                ______________________________________                                    

Thus, the activity of 13.5 wt. % "NAFION®" PFIEP/silica microcompositecatalyst was found to be almost an order of magnitude higher than thatof Amberlyst 15 and "NAFION®" NR50 and approximately 40 times higherthan that of sulfated zirconia. The selectivity of cyclohexyl acetatewas greater than 90 mole % for Amberlyst 15, "NAFION®" NR50, and 13.5wt. % "NAFION®" PFIEP/silica microcomposite catalysts while theselectivity was less than 50 mole % for sulfated zirconia.

Example 44 Formation of "TERATHANE®" Using the "NAFION®" PFIEP/SilicaCatalyst

A 300 mL "TEFLON®" lined Parr pressure reactor equipped with amechanical agitator, an internal 420 micron filter, and a feed pump wasloaded with 9 g "NAFION®" PFIEP/silica catalyst of Example 18 and filledthe rest of the way with a solution comprising 27.9 parts 3-methyltetrahydrofuran, 71.1 parts tetrahydrofuran, 6 parts acetic anhydrideand 0.6 parts acetic acid. The reactor was assembled, air bled, andfeeds started such that the average contact time in the reactor was 10hrs. The reaction was conducted at ambient temperature. Polymer wasproduced at 5.9% conversion at 4000 Mn. More catalyst (34 g) was addedfor a total of 43 g, and the reaction continued. Polymer was produced at20% conversion and 3500 Mn.

No analysis of 3-methyl THF content of polymer was done. This system ofreactants with 9 g "NAFION®" NR50, 10 hr contact time would produce45-50% conversions.

Example 45 80% "NAFION®" PFIEP/20% Silica Composite

40 g of TMOS, 7 g of water and 0.6 g of 0.04M HCl was stirred for 15mins. This was added to 1200 mL of a 5% "NAFION®" solution (which hadpreviously had 100 mL of 0.4M NaOH added over 5 mins. with stirring). Asoft gel was formed and the flask and contents were placed in an oven at95° C. under a nitrogen flow to dry. The hard glass-like product wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 h (with 500 mL of acid), followed by washingwith 500 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 times,and after the final wash the solid was dried under vacuum at 100° C. for24 h. Yield of dried product was 58 g.

Example 46 Organically Modified Silica/"NAFION®" PFIEP Composite SiO₂/SiO_(3/2) Me/"NAFION®" PFIEP

20 g of MeSi(OMe)₃ was mixed with 3 g of water and 0.3 g of 0.04M HCl.The solution was stirred for about 5 mins. A solution of 22 g of TMOS, 3g water and 0.3 g of 0.04M HCl (which was stirred for 3 mins.) was addedto the MeSi-containing solution. The combined clear silicon containingsolution was added to "NAFION®"/NaOH (60 mL of a 5% "NAFION®" solutionwhich contains 30 mL of 0.4M NaOH added over 1 min.) and the systemgelled in about 3-5 mins. The material was dried at 95° C. under anitrogen flow. The hard glass-like product was ground and passed througha 10-mesh screen, and then the material was stirred with 3.5M HCl for 1hour (with 100 mL of acid), followed by washing with 100 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times, and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Yieldof dried product was about 20 g. The illustrative example as describedin Example 28 was carried out with the exception that 1 g of thematerial from this example was used in the catalysis run. The conversionwas found to be 44% of heptene.

Example 47 PhSiO_(3/2) /MeSiO_(3/2) /Me₂ SiO/SiO₂ /"NAFION®" PFIEPComposite

5 g of PhSi(OMe)₃, 10 g MeSi(OMe)₃, 10 g Me₂ Si(OMe)₂ were mixed and 4 gof water and 0.3 g of 0.04M HCl was added and stirred. To this 22 g ofTMOS which was stirred with 0.3 g of 0.04M HCl and 3 g of water wasadded and the silicon containing solution was stirred for 15 mins. To 40g of the 5% "NAFION®" solution was added 25 ml of 0.4M NaOH over 1 min.Next the silicon containing solution was added to the stirred "NAFION®"solution and the mixture was left to gel. The material was dried at 95°C. under a nitrogen flow. The hard glass-like product was ground andpassed through a 10-mesh screen, and then the material was stirred with3.5M HCl for 1 hour (with 100 mL of acid, which also contained 25 mL ofethanol to ensure wetting), followed by washing with 100 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times, and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Theillustrative example as described in Example 28 was carried out with theexception that 1 g of the material from this example was used in thecatalysis run. The conversion was found to be 48% of heptene.

Example 48 Me₂ SiO/SiO₂ /"NAFION®" PFIEP Composite

20 g Me₂ Si(OMe)₂ were mixed and 3 g of water and 0.3 g of 0.04M HCl wasadded and stirred for 5 min. To this solution 25 g of TMOS which wasstirred with 0.3 g of 0.04M HCl and 3.5 g of water was added, and thesilicon containing solution was stirred for 15 mins. To 50 g of the 5%"NAFION®" solution was added 25 mL of 0.4M NaOH over 1 min. Next thesilicon containing solution was added to the stirred "NAFION®" solution,and the mixture was left to gel over about 30 seconds. The material wasdried at 95° C. under a nitrogen flow. The hard glass-like product wasground and passed through a 10-mesh screen, and then the material wasstirred with 3.5M HCl for 1 hour (with 100 mL of acid, which alsocontained 25 mL of ethanol to ensure wetting), followed by washing with100 mL of de-ionized water. The solid was collected by filtration.Acidification, washing and filtration were repeated a total of 5 timesand after the final wash the solid was dried under vacuum at 100° C. for24 h. The illustrative example as described in Example 28 was carriedout with the exception that 1 g of the material from this example wasused in the catalysis run. The conversion was found to be 37% ofheptene.

Example 49 Polydimethylsiloxane/Si/"NAFION®" PFIEP Composite

8 g of polydimethylsiloxane was added to 25 g of TMOS which was stirredwith 0.3 g of 0.04M HCl and 3.5 g of water was added and the siliconcontaining solution was stirred for 15 mins. To 50 g of the 5% "NAFION®"solution was added 25 mL of 0.4M NaOH over 1 min. Next the siliconcontaining solution was added to the stirred "NAFION®" solution, and themixture was left to gel over about 30 s. The material was dried at 95°C. under a nitrogen flow. The hard glass-like product was ground andpassed through a 10-mesh screen, and then the material was stirred with3.5M HCl for 1 hour (with 100 mL of acid, which also contained 25 mL ofethanol to ensure wetting), followed by washing with 100 mL ofde-ionized water. The solid was collected by filtration. Acidification,washing and filtration were repeated a total of 5 times, and after thefinal wash the solid was dried under vacuum at 100° C. for 24 h. Theillustrative example as described in Example 28 was carried out with theexception that 1 g of the material from this example was used in thecatalysis run. The conversion was found to be a 49% heptene.

Example 50 Comparative Example of "NAFION®" PFIEP Deposited upon aPre-formed Support

Catalysis Study

A sample of "NAFION®" PFIEP deposited on top of a silica gel support wasprepared according to the Illustrative Embodiment Ia of U.S. Pat. No.4,038,213. The silica used was a porous silica (A Divison silica 62).The surface area was 300 m² /g which is the same as described in U.S.Pat. No. 4,038,213, with a pore volume of 1.1 cc/gram. The porous silicasupport was treated with an alcohol solution of "NAFION®" (5% "NAFION®"PFIEP), and the alcohol was removed on a rotary evaporator leaving a 5%"NAFION®" on the silica catalyst. The support and "NAFION®" were driedat 150° C. before catalyst testing.

The illustrative example as described in Example 28 was carried out withthe exception that 2 g of the material from Example 50 was used in thecatalysis run. Thus, 2 g of a 5 wt. % "NAFION®" in silica was used,which had a total of 0.1 g of catalyst. The conversion was found to be24% of heptene.

By comparison, when using the same "NAFION®" loading, using a "NAFION®"PFIEP/silica catalyst which had been made in situ (and consisted ofhighly dispersed and entrapped "NAFION®" PFIEP) as described, forexample, in Examples 13-23 the conversion obtained was typically 85-99%.Thus, when 1 g of the material from Example 21 was used in the catalysisrun (the the total weight of "NAFION®" PFIEP being 0.1 g), theconversion was found to be 86% of heptene.

Microscopy Study

The microscopy was performed using a Hitachi S-5000SP microscope (ascanning electron microscope available from Hitachi Instruments, Japan)with a Norum EDS x-ray analysis. Particles, prepared according toExample 21, about 1-2 mm in size were mounted in an epoxy resin, whichwas set and the resin and particles were polished to give a polishedcross section of the particle, which reveals the interior of theparticle. Using EDS x-ray analysis in a spot mode (which analyzes asmall sub-micron area) showed the presence of Si, F, O and C all ofwhich were present across the whole interior part of the particle.Several areas within a particle and several different particles wereanalyzed and in all cases wherever Si was detected, F was also detectedshowing the intimate mixture of the two. No areas enriched in entirelySi or entirely F were observed. A uniform distribution of Si and F wasobserved.

Particles prepared according to the Illustrative Embodiment Ia of U.S.Pat. No. 4,038,213 were in contrast non-uniform. In most of the samplewhere Si was detected, no measurable F was found. On the very edge ofthe silica, a band of material rich in F was found but no silica,representing a film of the "NAFION®" PFIEP on the outer edge of thesilica particle, and not an intimate mixture of the "NAFION®" PFIEP. Thefilm could be observed visibly and varied in thickness from about 0.1 to4-5 microns on a particle of about 100 microns which showed no fluorinewithin it. The film (on the outer silica surface) was also absent insome areas. An intimate mixture of Si and was not observed.

Elemental x-ray maps (for Si, O and F) were prepared for the above twosamples. Using the procedure as described in Example 21, a uniformdistribution of all three elements was observed and was found within theentire particle of the microcomposite of the present invention.

An x-ray elemental map of the sample as prepared according to U.S. Pat.No. 4,038,213, showed a film of the fluorocarbon at the outer edge ofthe silica, with the bulk of the material being only silica.

Example 51 Catalytic Testing of "NAFION®" PFIEP/Silica Composites Usingthe Alkylation of Diphenyl Ether with Dodecene ILLUSTRATIVE EXAMPLE OFTHE PRESENT INVENTION

Both diphenyl ether and dodecene where dried over 3A molecular sievebefore use (dried for 24 hours). In a round bottom flask was added 17 gof diphenyl ether and 8.4 g of dodecene, and a "TEFLON®" coated magneticstirrer added. A reflux condenser was attached to the flask and a slowstream of nitrogen passed over the top of the reflux condenser tominimize moisture. The flask and contents were heated to 150° C. Asample of 1 g of the "NAFION®" PFIEP/silica catalyst as described inExample 13 was dried in vacuum at 150° C. for 15 hours. The driedmaterial was added to the diphenyl ether and dodecene mixture and thesolution stirred and left to react for exactly 2 hours at 150° C. Aftertwo hours a sample was removed of the dodecene and was measured usinggas chromatography. In the GC analysis dodecane was used as a standard.The conversion of diphenyl ether was measured to be greater than 99%,leaving less than 1% of the dodecene unreacted.

COMPARATIVE EXAMPLE

As a comparison experiment, the catalytic activity of 0.13 g of "NAFION"NR50 was tested. 0.13 g represents the same weight of "NAFION®" PFIEP astested above for the microcomposite. The exact same procedure was used,drying the NR50 at 150° C. for 16 hours and adding the NR50 to thestirred solution of dodecene (8.4 g) and diphenyl ether (17 g) at 150°C. After 2 hour reaction time the conversion was found to be about 5%,leaving 95% of the dodecene unreacted.

Example 52 60% "NAFION®" PFIEP in Silica

To 1200 g of a 5% "NAFION®" containing solution was added 150 g of 0.8MNaOH followed by 150 g of calcium carbonate powder. The flask andcontents were ultrasonicated for 2 minutes using a sonic horn.Separately to 135 g of tetraethoxysilane was added 37 ml of water and0.3 g of 3.5M HCl. The solution was stirred for 1 hour. The silicasolution was added to the "NAFION®" containing solution and the mixturewas left for 1 hour and then the material was dried in an oven at 95° C.for 2 days (with a stream of nitrogen purging through the oven),followed by drying in vacuum at 115° C. for 1 day. The solid was stirredwith 1 liter of 3.5M HCl overnight, followed by washing with 500 ml ofde-ionized water, and the solid collected by filtration. The solid wasfurther stirred with 500 ml of 3.5M HCl for 1 hour, filtered and washedwith 500 ml of de-ionized water and the process repeated a total of 5times. After the final wash the solid was dried under vacuum at 100° C.for 24 h.

Acylation Reaction

Benzoyl chloride and m-xylene and were dried over a molecular sievebefore use. In a round bottom flask was added 10.6 g of m-xylene and 7 gof benzoyl chloride, and a "TEFLON®" coated magnetic stirrer added. Areflux condenser was attached to the flask and a slow stream of nitrogenpassed over the top of the reflux condenser to minimize moisture. Theflask and contents were heated to 130° C. A sample of 0.17 gram of the"NAFION®" PFIEP/silica catalyst as described in this Example was driedin vacuum at 150° C. for 15 hours. The dried material was added to them-xylene and benzoyl chloride mixture and the solution stirred and leftto react for exactly 6 hours at 130° C. After six hours a sample wasremoved. In the GC analysis dodecane was used as a standard. Theconversion of benzoyl chloride was found to be 75%.

COMPARATIVE EXAMPLE

As a comparison experiment, the catalytic activity of 0.1 g of "NAFION®"NR50 PFIEP was tested. 0.1 g represents the same weight of "NAFION®"PFIEP as tested above for the composite. The exact same procedure wasused, drying the "NAFION®" NR50 PFIEP at 150° C. for 16 hours and addingthe "NAFION®" NR50 PFIEP to the stirred solution of m-xylene and benzoylchloride at 1300° C. After 6 hour reaction time the conversion was foundto be about 17%.

Example 53

The catalyst as prepared in Example 45 was used in this Example forcatalytic testing of "NAFION®" PFIEP/silica composites using theacylation of m-xylene with benzoyl chloride.

The m-xylene and benzoyl chloride were dried over molecular sieve beforeuse. In a round bottom flask was added 10.6 g of m-xylene and 7 g ofbenzoyl chloride, and a "TEFLON®" coated magnetic stirrer added. Areflux condenser was attached to the flask and a slow stream of nitrogenpassed over the top of the reflux condenser to minimize moisture. Theflask and contents were heated to 130° C. The "NAFION®" PFIEP/silicacomposition (about 5 grams) was ground to a fine powder using amortar-and pestle over about 10 minutes. A sample of 0.125 gram of the"NAFION®" PFIEP/silica catalyst as described in Example 45 was dried invacuum at 150° C. for 15 hours. The dried material was added to them-xylene and benzoyl chloride mixture and the solution stirred and leftto react for exactly 6 hours at 130° C. After six hours a sample wasremoved. In the GC analysis dodecane was used as a standard. Theconversion of benzoyl chloride was found to be 90%, as compared to aconversion of 17% for the comparative example as described above in theComparative Example of 52.

Example 54 40% "NAFION®" PFIEP in Silica

To 1200 ml of "NAFION®" was added 150 ml of 1.2M NaOH over about 10minutes. Separately 204 g of tetramethoxysilane, 32.6 g of water and 3 gof 0.04M HCl were mixed for 45 minutes and the silicon containingsolution was added to the "NAFION®" containing solution. The solutiongelled in about 1 minute and the flask and contents were placed in anoven at 100° C., with a nitrogen flow, for 2 days, followed by vacuumdrying for an additional day. The solid was ground and passed through a10 mesh screen and the solid was stirred with 3.5M HCl for 1 hour (with500 ml of acid), followed by washing with 500 ml of de-ionzied water,and the solid collected by filtration. This process was repeated a totalof 5 times and after the final wash the solid was dried under vacuum at100° C. for 24 h.

Acylation Reaction

The m-xylene and benzoyl chloride were dried over molecular sieve beforeuse. In a round bottom flask was added 10.6 g of m-xylene and 7 g ofbenzoyl chloride, and a "TEFLON®" coated magnetic stirrer added. Areflux condenser was attached to the flask and a slow stream of nitrogenpassed over the top of the reflux condenser to minimize moisture. Theflask and contents were heated to 130° C. A sample of 0.25 g of the"NAFION®" PFIEP/silica catalyst as described in this Example was driedin vacuum at 150° C. for 15 hours. The dried material was added to them-xylene and benzoyl chloride mixture and the solution stirred and leftto react for exactly 6 hours at 130° C. After six hours a sample wasremoved. In the GC analysis dodecane was used as a standard. Theconversion of benzoyl chloride was found to be 68% as compared to aconversion of 17% for the Comparative Example as described above in theComparative Example 52.

Example 55

To 350 ml of a 5% "NAFION®" containing solution was added 7.5 g of 8MNaOH. The solution was stirred for about 2 minutes. Separately, 12 ml ofwater and 1 ml of 0.04M HCl were added to 75 g of tetramethoxysilane.The solution was stirred for 45 minutes, and the silicon containingsolution was added to the "NAFION®" solution. The system gelled in about10 seconds and the flask and contents were dried in an oven at 95° C.for 2 days followed by drying in vacuum at 117° C. for a further day.The solid was ground and passed through a 10-mesh screen, and then thematerial was stirred with 3.5M HCl for 1 hour (with 250 ml of acid),followed by washing with 100 ml of de-ionized water, and the solidcollected by filtration. This process was repeated a total of 5 times,and after the final wash (with 1000 ml of de-ionized water) the solidwas dried under vacuum at 100° C. for 24 h.

Example 56

To 175 ml of a 5% "NAFION®" containing solution was added 2.5 g of 8MNaOH. The solution was stirred for about 2 minutes. Separately, 6 ml ofwater and 0.6 ml of 0.04M HCl were added to 42 g of tetramethoxysilane.The solution was stirred for 5 minutes and then added to the "NAFION®"solution. The system gelled in about 10 seconds and the flask andcontents were dried in an oven at 95° C. for 2 days followed by dryingin vacuum at 117° C. for a further day. The solid was ground and passedthrough a 10-mesh screen, and then the material was stirred with 3.5MHCl for 1 hour (with 250 ml of acid), followed by washing with 100 ml ofde-ionized water, and the solid collected by filtration. This processwas repeated a total of 5 times, and after the final wash (with 1000 mlof de-ionized water) the solid was dried under vacuum at 100° C. for 24h.

Example 57 1-Butene Isomerization in the Gas Phase

Solid acid catalyzed 1-butene isomerization to cis-2-butene,trans-2-butene and isobutene was carried out at temperatures between50-250° C. and ambient pressure in a 1/2" stainless steel reactor. Thetested acid catalyst of the present invention was the 13 wt % "NAFION®"PFIEP/silica microcomposite prepared in Example 16 which was comparedwith "NAFION®" NR50 and "AMBERLYST 15®". Typically, between 2.5-5.0 g ofcatalyst were loaded in the reactor. Prior to the reaction, catalystswere dried in vacuum oven at 150° C. for overnight except "AMBERLYST15®" was dried at 110° C. The reactant 1-butene was diluted with helium.The reaction mixture was analyzed by on-line gas chromatography (GC)equipped with a Flame Ionization Detector (FID) and a 25 m Plot columncoated with Al₂ O₃ /KCl.

The 1-butene isomerization results over the 2.5 g of the 13 wt %"NAFION®" PFIEP/silica microcomposite catalyst of the present inventionare listed in Table 1a and Table 1b below. Data in Table 1a show thatthe microcomposite prepared as in Example 16 is very efficient for thetitle reaction under mild conditions, even at 50° C., significant amountof 1-butene were converted to the 2-butenes. At 100° C., nearequilibrium n-butene distribution was obtained and extremely smallamounts of isobutene were formed. Isobutene as well as oligomers formedover the microcomposite catalyst were less than that produced from the"NAFION®" NR50 beads catalyst (see Table 2a below).

                  TABLE 1a                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 2.5 g 13 wt %             "NAFION ®" PFIEP/Silica Microcomposite Catalyst Under                     Ambient Pressure with Flow Rate of He = 1-Butene = 38 ml/min,                 WHSV of 1-Butene = 2 hr.sup.-1                                                   Temperature (° C.)                                                                                             % Butenes 50 100 150 200          ______________________________________                                                                                   250                                1-butene     38.0     15.8   15.3   21.2 25.0                                   trans-2-butene 33.9 54.9 5.4 45.6 42.4                                        cis-2-butene 28.1 29.3 31.0 31.8 31.9                                       isobutene    --       --     0.3    0.4  0.7                                  Oligomers    --       --     --     -2%  -5%                                  ______________________________________                                    

The reactant flow rate effect on the isomerziation over themicrocomposite was studied and the results are shown in Table 1b below.At 50° C., the thermodynamic equilibium distribution of n-butenes is4.1%, 70.5%, and 25.4% for 1-butene, trans-2-butene, and cis-2-butene,respectively. Data in Table 1b indicate that the equilibriumdistribution of n-butene can be readily obtained over the microcompositecatalyst at temperatures as low as 50° C.

                  TABLE 1b                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 2.5 g 13 wt %             "NAFION ®" PFIEP/Silica Composite Catalyst Under Ambient                  Pressure at 50° C. and Different WHSV of 1-Butene with Flow Ratio     of                                                                             He/1-Butene = 2/1                                                                 WHSV (hr.sup.-1)                                                                                            % Butenes 0.4 0.8 1.6                      ______________________________________                                        1-butene     6.9         14.9   37.8                                            trans-2-butene 66.3 56.2 34.6                                                 cis-2-butene 26.8 28.9 27.6                                                   isobutene -- -- --                                                          ______________________________________                                    

Comparison with "NAFION®" NR50

Table 2a below lists the results from 1-butene isomerization over the"NAFION®" NR50 beads at different temperatures. At 50° C. and the otherreaction conditions listed in Table 2a, 1-butene conversion was lessthan 1%. 1-Butene conversion increased gradually with increased reactiontemperature up to 200° C. The "NAFION®" NR50 beads melted at 250° C. andresulted in decreased activity. At the temperature where "NAFION®" NR50could effectively catalyze the 1-butene isomerization, about 200° C.,significant amount of oligomers of butene (C₈ +hydrocarbons) and thecracking products of those oligmers (C₁ -C₇ hydrocarbons) were alsoformed. In all cases, isobutene formation was negligible.

                  TABLE 2a                                                        ______________________________________                                        Product Distribtion for 1-Butene Isomerization over 5.0 g                       "NAFION ®" NR50 Catalyst Under Ambient Pressure                           with Flow Rate of He = 1-butene = 38 ml/min, WHSV of                          1-butene = 1 hr.sup.-1                                                          Temperature (° C.)                                                   % Butenes 50 100 150 200 250                                                ______________________________________                                        1-butene      >99.0   86.1   38.1   18.6 24.1                                   trans-2-butene -- 5.8 36.0 48.1 42.9                                          cis-2-butene <1.0 8.0 25.7 31.6 31.0                                          isobutene -- 0.1 0.2 1.7 3.0                                                Oligomers     --      --     -9%    -27% -36%                                 ______________________________________                                    

The effect of reactant flow rate, that is the weight hourly spacevelocity (WHSV) of butene (hr⁻¹) was investigated and the resultobtained at 150° C. was listed in Table 2b below. As the flow rate wasdecreased, the contact times of the reactant with solid catalystincreased, and consequently the 1-butene conversion to 2-butenesincreased. However, the thermodynamic equilibrium distribution ofbutenes were not reached over the "NAFION®" NR50 catalyst under thereaction conditions employed. Only small changes of 1-butene wererealized when the same study was carried out at 100° C. and almost noeffect of WHSV on 1-butene conversion was seen at 50° C.

                  TABLE 2b                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 5.0 g                      "NAFION ®" NR50 Catalyst Under Ambient Pressure at                        150° C. and Different WHSV of 1-Butene with Flow Ratio of             He/1-Butene = 2/1                                                                 WHSV (hr.sup.-1)                                                                                            % Butenes 0.2 0.4 0.8                      ______________________________________                                        1-butene    18.1         32.9   42.2                                            trans-2-butene 51.2 40.8 34.8                                                 cis-2-butene 30.2 26.0 23.0                                                   isobutene  0.5  0.3 --                                                      Oligomers   25%          12%    9%                                            ______________________________________                                    

Comparison with "AMBERLYST 15®"

1-Butene isomerization over commercial "AMBERLYST 15®" resin catalystwas also carried out under similar conditions for comparison. Thetemperature and flow rate effects are shown below in Table 3a and Table3b, repectively. The highest temperature studied was 100° C. because the"AMBERLYST 15®" is known to decompose and lose sulfonic groups atelevated temperatures (>130° C.). Data in Table 3a show that themacroporous "AMBERLYST 15®" catalyst (surface area .sup.˜ 34 m² /g) isan effective catalyst for the 1-butene isomerization to the linear2-butenes at the conditions employed and near equilibrium n-butenedistribution was obtained at 100° C. Similar to the results obtainedfrom the "NAFION®" NR50 and "NAFION®" PFIEP/silica microcompositecatalysts, isobutene formation was negligible in all cases.

                  TABLE 3a                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 5.0 g                      "AMBERLYST 15 ®" Catalyst Under Ambient Pressure                          with Flow Rate of He = 110 ml/min and 1-Butene = 90 ml/min,                   WHSV of 1-Butene = 2.5 hr.sup.-1                                                 Temperature (° C.)                                                  % Butenes 50 75 100                                                         ______________________________________                                        1-butene      69.8       10.7    8.2                                            trans-2-butene 17.1 62.2 62.8                                                 cis-2-butene 13.1 27.1 28.8                                                   isobutene -- -- 0.2                                                           Oligomers --  1.5% 4.0%                                                     ______________________________________                                    

Equilibrium was not reached at 50° C. even when very low flow rate of1-butene was used (Table 3b).

                  TABLE 3b                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 5.0 g                      "AMBERLYST 15 ®" Catalyst Under Ambient Pressure                          at 50° C. and Different WHSV of 1-Butene with Flow Ratio of           He/1-Butene = 1.2/1.0                                                            WHSV (hr-1)                                                                                                         % Butenes 0.28 0.44 1.03 2.08                                                2.50                                 ______________________________________                                        1-butene   24.7     31.0   53.0   67.8 69.8                                     trans-2-butene 51.2 46.2 29.3 19.2 17.1                                       cis-2-butene 24.1 22.8 17.7 13.0 13.1                                         isobutene -- -- -- -- --                                                    ______________________________________                                    

Example 58 1-Butene Isomerization in the Gas Phase

Solid acid catalyzed 1-butene isomerization to cis-2-butene,trans-2-butene and isobutene was carried out at temperatures between23-250° C. and ambient pressure with a 1/2" stainless steel reactor. A13 wt % "NAFION®" PFIEP/silica microcomposite as prepared in Example 16was dried at 150° C. overnight. The reactant 1-butene was diluted withhelium. The reaction mixture was analyzed by an on-line GC equipped witha FID detector and a 25 m Plot column coated with Al₂ O₃ /KCl.

The 1-butene isomerization results over the 13 wt % "NAFION®"PFIEP/silica microcomposite catalyst are shown in Tables 4a and 4b belowFIG. 1 is a graph showing the data from Table 4b plotting the reciprocalof WHSV.

                  TABLE 4a                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 5.0 g 13 wt %             "NAFION ®" PFIEP/Silica Microcomposite Catalyst Under Ambient             Pressure with Flow Rate of He = 105 ml/min and 1-Butene = 6 ml/min,           WHSV of 1-Butene = 0.16 hr.sup.-1                                                Temperature (° C.)                                                                                              % Butenes 50 100 150 200         ______________________________________                                                                                    250                               1-butene      10.3     7.8    10.5  23.0  16.1                                  trans-2-butene 62.4 63.2 57.9 54.6 50.8                                       cis-2-butene 27.3 28.6 29.9 29.9 31.2                                         isobutene --  0.1  0.4  1.1  1.5                                              Oligomers <1%  3%  3%  3%  3%                                               ______________________________________                                    

                  TABLE 4b                                                        ______________________________________                                        Product Distribution for 1-Butene Isomerization over 5.0 g 13 wt. %            "NAFION ®" PFIEP/Silica Microcomposite Catalyst Under Ambient             Pressure at 50° C. and Different WHSV of 1-Butene with Flow Ratio     of                                                                             He/1-Butene = 1.2/1                                                               WHSV (hr.sup.-1)                                                                                            % Butenes 1.0 1.6 2.5                      ______________________________________                                        1-butene     6.6          8.8    9.2                                            trans-2-butene 66.9 64.0 63.6                                                 cis-2-butene 26.5 27.2 27.2                                                   isobutene -- -- --                                                          ______________________________________                                    

Example 59 1-Heptene Isomerization in the Liquid Phase

Solid acid catalyzed 1-heptene isomerization to 2- and 3-heptenes(including cis- and trans-isomers of each) were carried out in theliquid phase at 60° C. Typically, 10 g of 1-heptene, 30 g of n-hexaneand 2 g of solid catalyst which was predried were charged to a two-neckflask with a magnetic stir bar for mixing. n-Hexane served as solventfor the reaction and internal standard for the GC analysis. Liquidsamples were taken at certain time intervals and analyzed by the GC thatwas described earlier. All of the five isomers were separated andidentified. Good material balances were obtained and formation ofoligomers was negligible. The 1-heptene conversions after 1 hr at 60° C.and the first order rate constants that were calculated from the data atlow 1-heptene conversions (<15%) are listed in Table 5 below. Similar tothe gas phase 1-butene isomerization, the 13 wt % "NAFION®" PFIEP/silicamicrocomposite as prepared in Example 16 was significantly more activethan the "NAFION®" NR50 beads and also was about 6 times more activethan the "AMBERLYST 15®" catalyst based on the unit weight of the solidcatalyst.

                  TABLE 5                                                         ______________________________________                                        1-Heptene Conversion (mol %) after 1 hr at 60° C. and the First         Order Rate Constant for 1-Heptene Isomerization over 2 g of                   Solid Acid Catalysts                                                                       13 wt %                                                                                              "NAFION ®"                              PFIEP/Silica "NAFION ®" "AMBERLYST                                       Catalyst Microcomposite NR50 15 ®"                                      ______________________________________                                        1-Heptene 86.4        3.8        20.6                                           Conv. (%)                                                                     Rate Constant 86.8 2.0 13.7                                                   (mM/gcat.hr)                                                                ______________________________________                                    

Example 60 1-Dodecene Isomerization in the Liquid Phase

1-Dodecene isomerization to its isomers was carried out in the liquidphase at 75° C. over 13 wt % "NAFION®" PFIEP/silica microcomposite asprepared in Example 16 and compared with "NAFION®" NR50 and "AMBERLYST15®" catalysts. For a typical run, 10 g of 1-dodecene, 30 g ofcyclohexane and 2 g of solid catalyst which was predried were charged toa two-neck flask with a magnetic stir bar for mixing. Cyclohexane servedas solvent for the reaction and internal standard for the GC analysis.Liquid samples were taken at certain time intervals and analyzed by theGC that was described earlier. There was no attempt to identify all ofthe n-dodecene isomers and only the 1-dodecene conversion was monitoredby following the decreasing of its GC peak area. Formation of oligomerswas negligible. The 1-dodecene conversions after 1 hr at 75° C. and thefirst order rate constants that were calculated from the data at low1-dodecene conversions (<15%) were listed in Table 6 below. Similar tothe gas phase 1-butene isomerization and the liquid phase 1-hepteneisomerization, the 13 wt % "NAFION®" PFIEP/silica microcomposite was themost active catalyst which was about 20 times more active than the"NAFION®" NR50 beads and was also about 4 times more active than the"AMBERLYST 15®" catalyst based on the unit weight of the solid catlayst.

                  TABLE 6                                                         ______________________________________                                        1-Dodecene Conversion (mol %) After 1 hr at 75° C. and the First        Order Rate Constant for 1-Dodecene Isomerization over 2 g of                  Solid Acid Catalysts                                                                       13 wt %                                                                                              "NAFION ®"                              PFIEP/Silica "NAFION ®" "AMBERLYST                                       Catalyst Microcomposite NR50 15 ®"                                      ______________________________________                                        1-Dodecene                                                                              76.6        13.6       57.7                                           Conv. (%)                                                                     Rate Constant 192.5 9.2 52.2                                                  (mM/gcat.hr)                                                                ______________________________________                                    

What is claimed is:
 1. An improved process for the alkylation of anaromatic compound with an olefin wherein the improvement comprisescontacting said aromatic compound and olefin with a catalytic porousmicrocomposite comprising perfluorinated ion-exchange polymer withpendant sulfonic and/or carboxylic acid groups entrapped within andhighly dispersed throughout a network of metal or metalloid oxide,wherein the weight percentage of perfluorinated ion-exchange polymer inthe microcomposite is from about 0.1 to about 90 percent, wherein thesize of the pores in the microcomposite is about 1 nm to about 75 nm,and wherein the microcomposite optionally further comprises pores havinga size in the range of about 75 nm to about 1000 nm.
 2. The process ofclaim 1 wherein the perfluorinated ion-exchange polymer contains pendantsulfonic acid groups and the metal or metalloid oxide is silica,alumina, titania, germania, zirconia, alumino-silicate,zirconyl-silicate, chromic oxide and/or iron oxide.
 3. The process ofclaim 2 wherein the metal or metalloid oxide is silica and saidmicrocomposite further comprises pores having a size in the range ofabout 75 nm to about 1000 nm.